WO2005121201A1 - Amphiphilic polymer compositions and their use - Google Patents

Amphiphilic polymer compositions and their use Download PDF

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Publication number
WO2005121201A1
WO2005121201A1 PCT/EP2005/006106 EP2005006106W WO2005121201A1 WO 2005121201 A1 WO2005121201 A1 WO 2005121201A1 EP 2005006106 W EP2005006106 W EP 2005006106W WO 2005121201 A1 WO2005121201 A1 WO 2005121201A1
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WIPO (PCT)
Prior art keywords
monomers
polymer
active ingredient
aqueous
water
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PCT/EP2005/006106
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German (de)
French (fr)
Inventor
Günter OETTER
Christian Krüger
Harald Köhle
Maria Scherer
Norbert Wagner
Matthias Bratz
Rainer Berghaus
Richard Van Gelder
Original Assignee
Basf Aktiengesellschaft
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP05748294A priority Critical patent/EP1756188B1/en
Priority to JP2007526277A priority patent/JP4718551B2/en
Priority to DE502005002170T priority patent/DE502005002170D1/en
Priority to CA2567660A priority patent/CA2567660C/en
Priority to PL05748294T priority patent/PL1756188T3/en
Priority to US11/628,609 priority patent/US7872067B2/en
Priority to BRPI0511688-0A priority patent/BRPI0511688A/en
Publication of WO2005121201A1 publication Critical patent/WO2005121201A1/en
Priority to IL179296A priority patent/IL179296A/en

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical

Definitions

  • the present invention relates to amphiphilic polymer compositions, to a process for their preparation and to their use for the preparation of aqueous active substance compositions of water-insoluble active compounds, in particular active ingredients for crop protection.
  • Active ingredients d. H. Substances which can already have a physiological effect even in low concentrations are often formulated in the form of aqueous active compound preparations.
  • the active ingredients used for pest control d. H. Insecticides, fungicides and herbicides, but also growth regulators, often formulated and sold as aqueous concentrates, which are diluted to the desired application concentration by adding a large amount of water before use (so-called "spray mixture")
  • Substances as well as food additives for example vitamins, provitamins, etc., have proven useful in the formulation of effect substances, ie low molecular weight compounds which already have a defined technical effect at a low application rate, eg dyes and UV stabilizers.
  • a principal problem with aqueous active substance preparations is the generally low water solubility of the active ingredients, which is frequently less than 10 g / l at 23 ° C./1013 mbar.
  • Aqueous formulations of such agents are therefore heterogeneous systems wherein the active ingredient is present as an emulsified or dispersed phase in a continuous aqueous phase.
  • emulsifiers or dispersants are used to stabilize these intrinsically metastable systems.
  • Their stabilizing effect is often unsatisfactory, so that deposition of the active ingredient, for example creaming or sedimentation of the active ingredient may occur, especially if the aqueous formulation is left for a prolonged period at elevated temperature and / or at strongly changing temperatures or in the vicinity of freezing is stored. This problem is particularly pronounced when the drug tends to crystallize.
  • organic solvents are also used to prepare aqueous formulations of water-insoluble active ingredients.
  • water-miscible solvents as solubility promoters, ie to increase the solubility of the active or effect substance in the aqueous phase.
  • Immiscible with water Solvents serve to convert a solid at application temperature active ingredient in a liquid phase, which can then emulsify more easily.
  • the active substance in the solvent droplets is molecularly dissolved in the emulsions and is therefore more readily available upon application and therefore more effective.
  • the use of larger amounts of organic solvents is not desirable due to the known VOC problem for occupational hygiene reasons, environmental aspects and sometimes also for toxicological reasons.
  • aqueous active substance preparations Another disadvantage of conventional aqueous active substance preparations is the comparatively large particle size of the active ingredient particles or active substance droplets suspended or emulsified in the aqueous phase, which is generally several ⁇ m.
  • aqueous formulations in which the active ingredient is present in the most finely divided form are desirable in order, on the one hand, to ensure a uniform distribution in the formulation and thus better handling and meterability and, at the same time, to increase the bioavailability of the active ingredient in the formulation.
  • Desirable are formulations in which the active ingredient-containing phase has mean particle sizes below 500 nm and in particular below 300 nm.
  • amphiphilic block copolymers to solubilize water-insoluble drugs in an aqueous vehicle has been proposed on several occasions.
  • the term “solubilization” refers to a stable uniform distribution of the water-insoluble active substance in the aqueous phase achieved using solubility-promoting substances (adjuvants), the particles of the disperse phase of active substance often being so small that they scarcely scatter visible light and the mixture therefore appears to be more or less transparent, the amphiphilic block copolymers generally having at least one hydrophilic polymer block and at least one hydrophobic polymer block.
  • US 2003/0009004 proposes for this purpose amphiphilic block copolymers comprising a hydrophilic polyethylenimine block and a hydrophobic block of biodegradable aliphatic polyester.
  • a disadvantage is that comparatively large amounts of polymer, based on the active ingredient, are required in order to obtain stable aqueous active substance preparations.
  • WO 02/82900 describes the use of amphiphilic block copolymers for preparing aqueous suspensions of water-insoluble crop protection active ingredients.
  • the block copolymers used are obtainable by "living" or “controlled” radical block copolymerization of ethylenically unsaturated monomers. Apart from the fact that such processes are comparatively complicated, the aqueous active substance formulations contain larger amounts of water-soluble organic solvents. In addition, the process requires the use of toxic transition metal catalysts that remain in the product. In addition, the block copolymers tend to brown.
  • block copolymers known in the art are not fully satisfactory, their preparation is very complicated is, the stability of the aqueous active compound preparations is unsatisfactory, the activity of the active ingredients is adversely affected or large amounts of polymer, based on the active ingredient are required, which in addition to increased costs may also adversely affect the use of such preparations.
  • the object of the present invention is therefore to provide substances which enable effective solubilization of water-insoluble active ingredients in an aqueous medium. These substances should be particularly suitable for providing aqueous active substance compositions of water-insoluble active ingredients which have no or only a very low content of volatile organic substances. Furthermore, a high stability of the aqueous active substance compositions prepared using these substances with respect to separation processes during long storage, when adding electrolyte and when diluted with water is desirable.
  • a polymer composition obtainable by reacting a) at least one hydrophobic polymer P1 which carries isocyanate-reactive functional groups R P1 and which is composed of ethylenically unsaturated monomers M1, comprising: a1) at least 10% by weight, based on the total amount of monomers M1, of monomers M1a of the general Formula I
  • X is oxygen or a group NR 4 ;
  • R 1 is Ci-Cio-alkyl, C 5 -C ⁇ o-cycloalkyl, phenyl or phenyl-C C 4 alkyl;
  • R 2 is hydrogen or C 1 -C 4 -alkyl;
  • R 3 is hydrogen or C 1 -C 4 -alkyl; and
  • R 4 is hydrogen or CC 4 alkyl; a2) up to 90% by weight, based on the total amount of monomers M1, of neutral, monoethylenically unsaturated monomers M1b whose solubility in water at 25 ° C.
  • the invention thus relates to the amphiphilic polymer compositions described here and to the process for their preparation.
  • amphiphilic polymer compositions according to the invention are advantageously suitable for stabilizing active substances and effect substances which are poorly or not soluble in water in the aqueous phase and therefore permit the preparation of aqueous formulations of such active substances and effect substances.
  • the block copolymers described in the prior art they can be used to solubilize large amounts of active ingredient, based on the polymer, in the aqueous phase.
  • the present invention therefore also relates to the use of the amphiphilic polymer compositions described here and below for stabilizing active substances and / or effect substances which are poorly or not soluble in water in an aqueous medium.
  • the present invention therefore also relates to the use of the amphiphilic polymer compositions described here for the preparation of formulations of active ingredients or effect substances which are insoluble or sparingly soluble in water and which are also referred to below as active ingredient composition or effect substance composition.
  • a poor solubility in this term means A solubility of the active or effect substance in water of below 10 g / l, often below 5 g / l, in particular below 1 g / l and especially below 0.1 g / l at 25 ° C and 1013 mbar.
  • the invention furthermore relates to active or effect compositions which comprise at least one active ingredient which is poorly soluble or insoluble in water and / or effect substance and at least one amphiphilic polymer composition, as described here and below.
  • the active substance or effect substance compositions according to the invention can be solid or liquid.
  • a preferred embodiment of such composition relates to an aqueous, i. liquid active ingredient composition comprising an aqueous medium as the continuous phase and at least one disperse phase containing at least one active ingredient and / or effect substance which has a solubility below 10 g / l in water at 25 ° C / 1013 mbar, and at least one amphiphilic polymer composition ,
  • aqueous active substance compositions prepared using the amphiphilic block copolymers according to the invention of active ingredients which are poorly soluble or insoluble in water comprise, in addition to an aqueous medium as the continuous phase, at least one phase containing effect or effect substance, in which the active substance or active substance phase contains. Effect substance and the amphiphilic polymer composition in the form of aggregates of drug or vantstoff and the polymer constituents of the amphiphilic polymer lyolyte composition. This active or effect-containing phase thus forms a disperse phase containing the active substance or the effect substance and at least one amphiphilic polymer composition according to the invention.
  • the disperse phase is extremely finely divided in these compositions, ie the particles of the disperse phase have particle sizes well below 1 .mu.m.
  • the average particle diameter is that determined by light scattering may not more than 500 nm, often not more than 300 nm and is often in the range of 10 to 300 nm, preferably in the range of 10 to 250 nm, in particular in the range of 20 to 200 nm or 20 to 150 nm, and particularly preferably in Range from 30 to 100 nm.
  • the phase particles may have even smaller average diameters up to an almost molecular dispersion with particle sizes below the limit detectable by light scattering (eg> 10 nm).
  • a further preferred embodiment of the invention relates to a non-aqueous, generally solid or semi-solid active ingredient composition which has at least one active ingredient and / or effect substance which has a solubility below 10 g / l in water at 25 ° C./1013 mbar, and at least one amphiphilic polymer composition containing substantially no or only minor amounts, d. H. Contains ⁇ 10 wt .-% water. As further constituents, these compositions may contain the typical auxiliaries and additives for the particular application.
  • compositions of the invention when diluted, provide aqueous preparations of the effect substance comprising an aqueous, continuous phase and at least one phase containing active substance with average particle sizes well below 1 ⁇ m, typically no longer 500 nm, often not more than 300 nm, z.
  • aqueous preparations of the effect substance comprising an aqueous, continuous phase and at least one phase containing active substance with average particle sizes well below 1 ⁇ m, typically no longer 500 nm, often not more than 300 nm, z.
  • average particle sizes well below 1 ⁇ m typically no longer 500 nm, often not more than 300 nm, z.
  • 10 to 300 nm preferably in the range of 10 to 250 nm, in particular in the range of 20 to 200 nm or 20 to 150 nm and particularly preferably in the range of 30 to 100 nm.
  • the particle sizes given here are weight-average particle sizes, as can be determined by dynamic light scattering. Methods for this purpose are familiar to the person skilled in the art, for example from H. Wiese in D. Distler, Aqueous Polymer Dispersions, Wiley-VCH 1999, Chapter 4.2.1, p 40ff and literature cited therein and H. Auweter, D. Horn, J. Colloid Interf , Be. 105 (1985) 399, D. Lie, D. Horn, Colloid Polym. Be. 269 (1991) 704 or H. Wiese, D. Horn, J. Chem. Phys. 94 (1991) 6429.
  • aqueous medium and “aqueous phase” here and below include water, aqueous mixtures of water with up to 10 wt .-%, based on the mixture, of organic solvents which are miscible with water, and solutions of solids in water or in the aqueous mixtures.
  • water-miscible solvents include C 3 -C ketones, such as acetone and methyl ethyl ketone, cyclic ethers, such as dioxane and tetrahydrofuran, C 1 -C 4 -alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert.
  • Butanol, polyols and their mono- and dimethyl ethers such as glycol, propanediol, ethylene glycol monomethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, glycerol, furthermore C 2 -C 3 -nitriles such as acetonitrile and propionitrile, dimethylsulfoxide, dimethylformamide, formamide, acetamide, dimethylacetamide, butyrolactone, 2-pyrrolidone and N-methylpyrrolidone.
  • C 2 -C 3 -nitriles such as acetonitrile and propionitrile, dimethylsulfoxide, dimethylformamide, formamide, acetamide, dimethylacetamide, butyrolactone, 2-pyrrolidone and N-methylpyrrolidone.
  • aqueous active compound compositions according to the invention are distinguished by extremely high stability against segregation. You can without decongestion over a longer period of several months even at elevated
  • compositions have a high tolerance to electrolytes.
  • the activity of the active ingredients is increased compared to conventional aqueous formulations.
  • aqueous active substance compositions according to the invention also low in solvents (content of volatile solvents ⁇ 10 wt .-%, based on the weight of the active ingredient composition) or even solvent-free (content of volatile solvents ⁇ 1% by weight, based on the weight the active ingredient composition) can be formulated.
  • the hydrophobic polymers P1 used to prepare the amphiphilic polymer composition according to the invention and the hydrophilic polymers P2 have isocyanate-reactive functional groups R P1 and R P2 , respectively, which react with the isocyanate group of the compound V to form bonds.
  • suitable functional groups are hydroxyl groups, mercapto groups (SH) and primary and secondary amino groups.
  • Preferred functional groups are hydroxyl groups, in particular hydroxyl groups bound to an aliphatic or eycloaliphatic C atom.
  • reaction of V with the polymer P1 and the polymer P2 at least partially forms block copolymers which comprise both at least one hydrophobic polymer block which is different from the hydrophobic polymer P1, as well as having at least one hydrophilic polymer block derived from the hydrophilic polymer P2.
  • the blocks are not linked directly to each other, but via a linker, which at least two Has urethane and / or urea groups.
  • amphiphilic polymer compositions obtained generally still to a lesser extent unreacted polymers P1 and / or P2 and symmetrical reaction products having either polymer blocks exclusively derived from polymers P1 or polymer blocks derived exclusively from polymers P2 , Nevertheless, the beneficial amphiphilic properties of the polymer composition are preserved.
  • Suitable hydrophobic polymers P1 are in principle all polymers made up of ethylenically unsaturated monomers M1, which contain at least 10% by weight, preferably at least 30% by weight, in particular at least 50% by weight, particularly preferably at least 60% by weight .-%, based on the total amount of monomers M1, monomers M1a in copolymerized form and having the required number of reactive groups R P1 .
  • Preferred monomers M1a are those in which R 3 in formula I is hydrogen.
  • R 2 is preferably hydrogen or methyl.
  • X is preferably O, NH, NCH 3 or NC 2 H 5 .
  • R 1 is C 1 -C 10 -al
  • Particularly preferred monomers M1a are therefore the esters of acrylic acid with
  • Preferred monomers M1a are also the N- (C 2 -C ⁇ o-alkyl) amides of acrylic acid and methacrylic acid and the N- (-CC 2 alkyl) -N- (C 2 -C 10 alkyl) amides of acrylic acid and the methacrylic acid, z.
  • the hydrophobic polymer P1 may also comprise monomers M1b other than the monomers M1a in an amount of up to 90% by weight, preferably up to 70% by weight, in particular up to 50% by weight and particularly preferably up to 40% by weight .-%, based on the total amount of monomers M1 in copolymerized form.
  • monomers M1b other than the monomers M1a in an amount of up to 90% by weight, preferably up to 70% by weight, in particular up to 50% by weight and particularly preferably up to 40% by weight .-%, based on the total amount of monomers M1 in copolymerized form.
  • monomers M1b other than the monomers M1a in an amount of up to 90% by weight, preferably up to 70% by weight, in particular up to 50% by weight and particularly preferably up to 40% by weight .-%, based on the total amount of monomers M1 in copolymerized form.
  • These are monoethylenically unsaturated monomers having a water solubility ⁇ 50
  • Examples of such monomers M1 b are vinylaromatic monomers, such as styrene, ⁇ -methylstyrene, vinyltoluene, etc., olefins having 2 to 10 C atoms, preferably ⁇ -olefins having 3 to 10 C atoms, such as propene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene, vinyl esters of aliphatic carboxylic acids such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl nonanoate, vinyl decanoate, vinyl laurate and vinyl stearate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, halogenated olefins such as vinyl chloride, Cn-C 2 o-alkyl esters of monoethylenically unsaturated monocarboxylic acids having preferably 3 to 6 C atoms, for.
  • Cn-C ⁇ alkyl acrylates and C ⁇ -C 2 o-alkyl methacrylates such as lauryl acrylate, lauryl methacrylate, Isotridecylacrylat, Isotridecylmethacrylat, stearyl acrylate, stearyl methacrylate, di-CrC 20 alkyl ethyleniseh unsaturated dicarboxylic acids having preferably 4 to 8 carbon atoms, eg , B.
  • Di-CrC 20 alkyl esters of fumaric acid and maleic acid such as dimethyl fumarate, dimethyl maleate, dibutyl and dibutyl maleate, glycidyl esters of monoethylenically unsaturated monocarboxylic acids having preferably 3 to 6 carbon atoms, such as glycidyl acrylate and glycidyl methacrylate.
  • Preferred monomers M1 b are vinylaromatic monomers and, among these, in particular styrene.
  • the proportion of the monomers M1 b is 1 to 90% by weight, preferably 5 to 70% by weight, in particular 7 to 50% by weight and particularly preferably 10 to 40% by weight, based on the total amount the monomers M1.
  • the total amount of monomers M1a and M1b is preferably at least 80% by weight, in particular at least 90% by weight and particularly preferably at least 95% by weight of the monomers M1.
  • the polymers P1 can be up to 30 wt .-%, often not more than 20 wt .-%, in particular not more than 10 wt .-% or not more than 5 wt .-%, based to the total amount of monomers M1, ethyleniseh unsaturated monomers M1c, which are different from the monomers M1a and M1b, in copolymerized form.
  • the monomers M1c are preferably selected from neutral monoethylenically unsaturated monomers M1c.1 whose water solubility at 25 ° C. is at least 50 g / l and in particular at least 100 g / l and monoethylenically unsaturated monomers M1c.2 which carry at least one ionic or ionizable group.
  • Examples of monomers M1c.1 are the amides of the abovementioned ethylenically unsaturated carboxylic acids, in particular acrylamide and methacrylamide, and
  • N-hydroxyalkylamides especially N-hydroxymethylamides of the aforementioned ethyleniseh unsaturated carboxylic acids, in particular N-methylolacrylamide and N-methylolmethacrylamide, ethyleniseh unsaturated nitriles such as methacrylonitrile and acrylonitrile, hydroxyalkyl esters of the aforementioned ⁇ , ß-ethylenically unsaturated C 3 -C 8 monocarboxylic acids and the C 4 -C 8 -dicarboxylic acids, in particular hydroxyethyl acrylate, hydroxyethyl methacrylate, 2- and 3-hydroxypropyl acrylate, 2- and 3-hydroxypropyl methacrylate, vinyl and allyl ethers of polyethylene glycols or alkylpolyethylene glycols, esters of the abovementioned monoethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 4 -polyal
  • the monomers M1c.1 also include N-vinylamides such as N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam. Monomers M1c.1 furthermore include monomers carrying urea groups, such as
  • N- (2-acrylamidoethyl) -imidazolin-2-one and N- (2-methacrylamidoethyl) -imidazolin-2-one and aldehyde- or keto-containing monomers such as 3- (acrylamido) -3-methylbutan-2-one (diacetone acrylamide ), 3- (methacrylamido) -3-methylbutan-2-one, 2,4-dioxapentyl acrylate and 2,4-dioxapentyl methacrylate.
  • the proportion of the monomers M1 c.1 is preferably not more than 20 wt .-%, and in particular not more than 10 wt .-%, z. B. 0.1 to 10 and in particular 0.5 to 5 wt .-%, based on the total amount of the monomers M1 account.
  • the monomers M1c.2 include, in particular, monoethylenically unsaturated monomers M1c.2s which have at least one acid group or at least one anionic group, in particular monomers which have a sulfonic acid group, a phosphonic acid group or one or two carboxylic acid groups, and the salts of such monomers, in particular the alkali metal salts, e.g. As the sodium or potassium salts and ammonium salts.
  • ethyleniseh unsaturated sulfonic acids in particular vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloxyethanesulfonic acid and 2-methacryloxyethanesulfonic acid, 3-acryloxy- and 3-methacryloxypropanesulfonic acid, vinylbenzenesulfonic acid and its salts, ethyleniseh unsaturated phosphonic acids, such as vinylphosphonic acid and vinylphosphonic acid.
  • the proportion of monomers M1c.2s is often not more than 20 wt .-%, z. B. 0.1 to 20 wt .-% and in particular 0.5 to 15% by weight, based on the total amount of the monomers M1, make up.
  • the polymer P1 contains in copolymerized form no or not more than 0.1% by weight of monomers M1c.2s.
  • the monomers M1c.2 furthermore include monoethylenically unsaturated monomers M1c.2k which have at least one cationic group and / or at least one group which can be protonated in the aqueous.
  • the monomers M1c.2k include, in particular, those which have a protonatable amino group, a quaternary ammonium group, a protonatable imino group or a quaternized imino group. Examples of monomers having a protonatable imino group are N-vinylimidazole and vinylpyridine.
  • Examples of monomers having a quaternized imino group are N-alkylvinylpyridinium salts and N-alkyl-N'-vinylimidazolinium salts such as N-methyl-N'-vinylimidazolinium chloride or metosulphate.
  • the monomers M1c.2k in particular the monomers of the general formula II are preferred
  • R 5 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl
  • R 6 , R 7 are independently C 1 -C 4 -alkyl, in particular methyl, and
  • R 8 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl
  • A is C 2 -C 8 alkylene, e.g. B. 1, 2-ethanediyl, 1, 2- or 1, 3-propanediyl, 1, 4-butanediyl or 2-methyl-1, 2-propanediyl, which is optionally interrupted by 1, 2 or 3 non-adjacent oxygen atoms is and
  • Examples of such monomers M1c.2k are 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dimethylamino) ethyl acrylamide, 3- (N, N-dimethylamino) propylacrylamide, 3- (N, N-dimethylamino) propylmethacrylamide, 2- (N, N-dimethylamino) ethylmethacrylamide,
  • the proportion of the monomers M1 c.2k is advantageously not more than 20% by weight, e.g. 0.1 to 20 wt .-%, in particular 0.5 to 15 wt .-%, and especially 1 to 10% by weight, based on the total amount of the monomers M1.
  • the polymer P1 contains in copolymerized form no or not more than 0.1% by weight of monomers M1c.2k.
  • the monomers M1c also include monomers M1c.3, which have two or more non-conjugated ethyleniseh unsaturated double bonds.
  • the proportion of such monomers M1c.3 will generally be not more than 2% by weight and in particular not more than 0.5% by weight, based on the total monomer amount M1.
  • Examples thereof are vinyl and allyl esters of monoethylenically unsaturated carboxylic acids, such as allyl acrylate and allyl methacrylate, di- and polyacrylates of diols or polyols, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol trimethacrylate, tris (hydroxymethyl ) ethane triacrylate and trimethacrylate, pentaerythritol triacrylate and trimethacrylate, and also the allyl and methallyl esters of polyfunctional carboxylic acids, such as diallyl maleate, diallyl fumarate, diallyl phthalate.
  • di- and polyacrylates of diols or polyols such as
  • Typical monomers M1c.3 are also compounds such as divinylbenzene, divinylurea, diallylurea, triallyl cyanurate, N, N'-divinyl and N, N'-diallylimidazolidin-2-one, as well as methylenebisacrylamide and methylenebismethacrylamide.
  • the polymers P1 carry reactive functional groups R P1 which react with the isocyanate groups to form bonds.
  • the average number of such groups per polymer molecule (functionality) is generally not more than two and is preferably in the range of 0.3 to 1.8, in particular in the range of 0.5 to 1.5, and especially in the range of 0, 6 to 1, 4.
  • the functional group R P1 can be found in the Polymer chain can be arranged and is preferably at the end of the polymer chain.
  • the hydrophobic polymer P1 preferably has a number-average molecular weight in the range from 500 to 20,000 daltons and in particular in the range from 1500 to 15,000 daltons.
  • Polymers P1 are known in principle from the prior art, for example from US 5,556,918 and EP-A 742 238. They are generally prepared by free-radically initiated solution polymerization of the monomers M1 in the presence of an initiator and optionally a regulator, with the proviso that the Initiator at disintegration
  • Hydroxyl radical (OH radical) and / or the regulator contains an OH group or an NH 2 group.
  • Suitable initiators are organic hydroperoxides such as tert-butyl hydroperoxide, tetrahydrofuran hydroperoxide, cumene hydroperoxide or 2,2'-
  • Suitable regulators are amino alcohols, aminophenols and, in particular, thioalkanols, such as 3-hydroxypropanethiol, 2-hydroxyethyl-3-mercaptopropionic acid ester and above all 2-hydroxyethanethiol (mercaptoethanol).
  • the polymerization can also be carried out in the presence of a conventional initiator, for example a conventional azo starter or an organic peroxide such as azobis (isobutyronitrile), di (tert-butyl) peroxide, didecanoyl peroxide, dibenzoyl peroxide, Peracetic acid tert-butyl ester or 2-methylperpropionic acid tert-butyl ester.
  • a conventional initiator for example a conventional azo starter or an organic peroxide such as azobis (isobutyronitrile), di (tert-butyl) peroxide, didecanoyl peroxide, dibenzoyl peroxide, Peracetic acid tert-butyl ester or 2-methylperpropionic acid tert-butyl ester.
  • the regulator is generally added in an amount of from 0.1 to 5% by weight, frequently from 0.2 to 4% by weight and in particular from 0.5 to 3 % By weight, based on the
  • Initiators are usually added in an amount of 0.05 to 5 wt .-%, often 0.1 to 4 wt .-% and particularly preferably in an amount of 0.2 to 3 wt .-%, based on the polymerizing monomers M1 used.
  • Initiators are usually added in an amount of 0.05 to 5 wt .-%, often 0.1 to 4 wt .-% and particularly preferably in an amount of 0.2 to 3 wt .-%, based on the polymerizing monomers M1 used.
  • Hydrophilic polymers P2 which have reactive groups R P2 are known in principle to the person skilled in the art. These are usually polymers that are individually soluble in water. The water solubility of the polymers can be controlled by neutral hydrophilic groups such as carboxamide groups, ether groups, lactam groups, oxazolidine groups, by anionic groups or acidic groups, eg. As carboxylate groups, sulfonate groups or phosphate groups, by basic groups, for. Example by primary or secondary amino groups, imidazole groups, pyridine, or cationic groups, for example quaternized ammonium groups, quaternized pyridine groups or quaternized imidazole groups.
  • nonionic hydrophilic polymers P2 anionic or acidic polymers P2 and basic or cationic polymers P2.
  • the polymer P2 is a nonionic polymer, ie the proportion of ionic groups or acidic or basic groups is not more than 0.5 mol / kg of polymer P2 and in particular not more than 0.1 mol / kg of polymer P2.
  • nonionic polymers P2 are: aliphatic polyethers which are composed of at least 50% by weight and in particular at least 70% by weight of ethylene oxide units,
  • Suitable monomers M2a are the monomers M1c.1 mentioned as monomers, in particular N-vinyllactams such as N-vinylpyrrolidone and N-vinylcaprolactam, the aforementioned amides of monoethylenically unsaturated monocarboxylic acids such as methacrylamide, acrylamide, the aforementioned hydroxyalkyl esters of monoethylenically unsaturated monocarboxylic acids such as hydroxyethyl acrylate and hydroxyethyl methacrylate, vinyl and Allyl esters of polyethylene glycol and of alkyl polyethylene glycols and the esters of acrylic acid and methacrylic acid with polyethylene glycols or alkyl polyethylene glycols.
  • N-vinyllactams such as N-vinylpyrrolidone and N-vinylcaprolactam
  • the aforementioned amides of monoethylenically unsaturated monocarboxylic acids such as methacryl
  • Poly (2-methyloxazolines) and poly (2-ethyloxazolines), and poly ( ⁇ -hydroxycarboxylic acid) esters such as polyglycolide and polylactide.
  • suitable anionic polymers P2 are those which contain at least 30% by weight and preferably at least 50% by weight, based on the total weight of the polymer P2, of monoethylenically unsaturated monomers M2b in copolymerized form, which contain an acid group, eg. A carboxyl group, a sulfonic acid group, a phosphate group or a phosphonic acid group.
  • suitable monomers M2b are the monomers M1c.2s mentioned in connection with the polymers P1, z. B.
  • ß-ethylenically unsaturated mono- and dicarboxylic acids such as acrylic acid, methacrylic acid, vinylacetic acid, monoethylenically unsaturated sulfonic acids such as nylsulfonate, methallylsulfonate, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and 2-acryloxyethylsulfonic acid, ethyleniseh unsaturated phosphonic acids such as vinylphosphonate, allylphosphonate, methallylphosphonate, 2-acrylamido-2-methylpropanephosphonic acid and 2-acryloxyethylphosphonate.
  • monoethylenically unsaturated sulfonic acids such as nylsulfonate, methallylsulfonate, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and 2-acryloxyethylsul
  • suitable anionic polymers P2 may contain, in copolymerized form, up to 50% by weight and in particular up to 30% by weight of monomers M1a and M1b and up to 70% by weight of monomers M2a.
  • Suitable cationic polymers P2 are homopolymers and copolymers of the aforementioned monoethylenically unsaturated monomers M1 c.2k, and also copolymers of the monomers M1c.2k with the monoethylenically unsaturated neutral monomers M1c.1.
  • polymers P2 preference is given in particular to those which have a functionality F2 in the range from 0.5 to 3 and in particular in the range from 0.6 to 2.5 with respect to the functional groups R P2 .
  • the number-average molecular weight of the polymers P2 is preferably in the range from 500 to 20,000 daltons and in particular in the range from 800 to 15,000 daltons.
  • polymers P2 preference is given in particular to aliphatic polyethers which are at least 50% by weight and in particular at least 70% by weight and more preferably at least 90% by weight, based on their total weight, of ethylene oxide units.
  • the aliphatic polyethers may have structural units derived from C 3 -C 4 -alkylene oxides.
  • the polyethers may also have an end group other than hydrogen.
  • Particularly preferred polyethers are, in particular, those of the general formula III R a -X- (CHR b -CH 2 -O) p -H (IM)
  • R a is hydrogen, C 1 -C 20 -alkyl or benzyl, X is oxygen or NH,
  • R b is hydrogen or methyl, where at least 50 mol%, in particular at least 70 mol% and preferably at least 90 mol% of the groups R 2 are hydrogen, p is an integer whose mean value is in the range from 10 to 500, preferably 20 to 250 and in particular 25 to 100 (number average).
  • Suitable hydrophilic polymers P2 are known to the person skilled in the art and are largely commercially available, for example under the trade names Pluriol® and Pluronic® (polyether from BASF Aktiengesellschaft), Sokalan®, Kollidon® (homo- and copolymers of the monomers M2a, M2b and M1c.2k) , or can be made by routine methods.
  • the total amount of hydrophobic polymers P1 on the amphiphilic polymer composition i. the total amount of reacted and unreacted polymer P1 is preferably from 9 to 90 and in particular from 20 to 68% by weight of the total weight of polymer P1, polymer P2 and compound V.
  • the total amount of hydrophobic polymers P2 on the amphiphilic polymer composition i. the total amount of reacted and unreacted polymer P2 is preferably from 9 to 90 and in particular from 30 to 78% by weight of the total weight of polymer P1, polymer P2 and compound V.
  • the total amount of compound V on the amphiphilic polymer composition i. the total amount of compound V used is preferably from 1 to 20 and in particular from 2 to 15% by weight of the total weight of polymer P1, polymer P2 and compound V.
  • the weight ratio of polymer P1 and P2 in the amphiphilic polymer composition is preferably in the range from 1:10 to 10: 1 and in particular in the range from 1: 4 to 2.2: 1.
  • Suitable compounds V having a functionality with regard to the isocyanate groups of at least 1.5, in particular 1.5 to 4.5 and especially 1.8 to 3.5 include aliphatic, cycloaliphatic and aromatic di- and polyisocyanates and the isocyanurate, Allophanates, urethdiones and biurets of aliphatic, cycloaliphatic and aromatic diisocyanates.
  • the compounds V have on average from 1.8 to 3.5 isocyanate groups per molecule.
  • suitable compounds V are aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanates, commercially available mixtures of toluene-2,4- and 2,6-diisocyanate (TDI), n-phenylene diisocyanate, 3,3'-diphenyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, cumene 2,4-diisocyanate, 1, 5-naphthalene diisocyanate, p-xylylene diisocyanate, p-phenylene diisocyanate, 4-methoxy-1,3-phenylene diisocyan
  • 1, 4-tetramethylene diisocyanate, 1, 10-decamethylene diisocyanate and cycloaliphatic diisocyanates such as isophorone diisocyanate (IPDI), cyclohexylene-1, 2-diisocyanate, cyclohexyl-1, 4-diisocyanate and bis (4,4'-isocyanatocyclohexyl) methane.
  • IPDI isophorone diisocyanate
  • cyclohexylene-1 2-diisocyanate
  • 2-diisocyanate cyclohexyl-1
  • 4-diisocyanate bis (4,4'-isocyanatocyclohexyl) methane.
  • diisocyanates preference is given to those whose isocyanate groups differ in their reactivity, such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, mixtures thereof and cis and
  • a biuret or an isocyanurate of an aliphatic or cycloaliphatic diisocyanate compound for example the cyanurate of tetramethylene diisocyanate or of hexamethylene diisocyanate, is used to prepare the amphiphilic polymer composition according to the invention.
  • the hydrophobic polymer P1 and the hydrophilic polymer P2 are reacted successively or simultaneously under reaction conditions with the compound V, under which the groups R P1 and R P2 react with the isocyanate groups to form bonds.
  • the reaction may be carried out in the absence or in the presence of small amounts thereof, more preferably catalysts which promote the formation of urethanes or ureas.
  • Suitable catalysts are, for example, tertiary amines, for.
  • triethylamine tri-n-propylamine, N-methylpyrrolidine, N-methylpiperidine and diazabicyclooctane (DABCO)
  • organotin compounds especially dialkyltin (IV) salts of aliphatic carboxylic acids such as dibutyltin dilaurate and dibutyltin dioctoate, tin (II) dialkanoate such as tin dioctoate, and cesium salts like cesium acetate.
  • the catalyst is added in an amount of not more than 0.1% by weight, based on the compound V, e.g. B. in an amount of 0.01 to 0.1 wt .-%, in particular up to 0.05 wt .-% use.
  • the required reaction temperatures are naturally dependent on the reactivity of the functional group R P1 or R P2 and the isocyanate compound V and, if used, on the type and amount of catalyst used. It is usually in the range of 10 to 120 ° C and in particular in the range of 15 to 85 ° C. It goes without saying that the reaction of the polymers P1 and P2 with the isocyanate compound V takes place in the absence of moisture (water content of preferably ⁇ 10000 ppm and in particular ⁇ 2000 ppm).
  • the reaction can be carried out in bulk or in an organic solvent which is inert to the isocyanate groups of the compound V.
  • suitable solvents are aliphatic ketones such as acetone, methyl ethyl ketone, cyclohexanone, alkyl esters of aliphatic carboxylic acids such as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-butyl acetate, alicyclic and cyclic ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether,
  • Tetrahydrofuran aromatic, aliphatic and alicyclic hydrocarbons such as toluene, xylenes, hexane, cyclohexane, and N-alkyl lactams such as N-methylpyrrolidone and mixtures of these solvents.
  • reaction of the polymer P1 and the polymer P2 with the compound V can be carried out successively or simultaneously, i. H. Polymer P1 and P2 can be reacted sequentially or simultaneously with the compound V.
  • both the polymer P1 with the compound V and then the polymer P2 with the compound V can be reacted first and vice versa.
  • the reaction is preferably carried out in such a way that after completion of the reaction with the first polymer P1 or P2 at least 10 mol% to 90 mol%, in particular 20 mol% to 80 mol% of the isocyanate groups in V have reacted with the functional groups R 1 or R 2 and 10 to 90 mol%, in particular 20 to 80 mol% of the isocyanate groups present are still present. Subsequently, the reaction is then carried out with the second polymer P1 or P2.
  • the first polymer P1 or P2 is used in an amount such that the molar ratio of reactive groups R P1 or R P2 to the number of isocyanate groups per molecule V is in the range from 0.1: 1 to 0.9: 1 and in particular in the range of 0.2: 1 to 0.8: 1.
  • the product thus obtained is then reacted with the second polymer, the second polymer P1 or P2 preferably being used in an amount such that the total amount of reactive groups R P1 + R P2 is at least equal to the number of isocyanate groups of compound V equivalent.
  • the ratio R P1 + R P2 to the total amount of isocyanate groups will not exceed a value of 1.2: 1.
  • the polymers P1 and P2 are reacted simultaneously with the isocyanate compound V, it is preferable to use the polymers P1 and P2 in an amount such that the molar ratio of reactive groups R P1 + R P2 to the isocyanate groups is at least 1: 1.
  • the ratio R P1 + R P2 to the total amount of isocyanate groups will not exceed a value of 1.2: 1.
  • the isocyanate compound V can be used as such in the reaction. However, it is also possible to use the isocyanate compound V in a form in which a part of the isocyanate groups is reversibly blocked by a protective group.
  • Compounds which block (cap or protect) isocyanate groups have been described many times in the literature (see, for example, BZW Wicks, Prog. Org. Coat 3 (1975) 73-99 and 9 (1981) 3-28 or Houben-Weyl , Methods of Organic Chemistry Bd. XI V / 2, p. 61 ff., Georg Thieme Verlag, Stuttgart 1963).
  • blocking agents of isocyanate groups include phenols, caprolactam, imidazoles, pyrazoles, pyrazolinones, 1,2,4-triazoles, diketopiperazines, malonic esters and oximes. To achieve the success of the invention, however, the use of partially reversibly blocked isocyanates is not required.
  • the hydrophobic polymer P1 in a first reaction step, is prepared by free-radical solvent polymerization in the manner described above and carries out the reaction with the isocyanate V in the liquid reaction mixture thus obtained, without the polymer Isolate P1 in advance.
  • the reaction mixture obtained is then reacted with the polymer P2, preferably a polyether.
  • the desired amount of polymer P2 can be added to the polymer P1 thus prepared and then the reaction with the compound V can be carried out.
  • the polymer composition obtained according to the invention can be isolated from the reaction mixture. However, it is also possible to use the reaction mixture as such.
  • the solvent used to prepare the polymer composition is partially or completely replaced by water to give an aqueous dispersion of the amphiphilic polymer composition.
  • This can be effected, for example, by first distilling off the solvent and then dispersing the residue in water or in an aqueous medium.
  • water may be added water to the solution of the polymer composition and remove the solvent following or in parallel with the addition of the water.
  • the preparation of the active ingredient or effect substance composition according to the invention can take place in different ways.
  • the preparation of the active ingredient composition according to the invention comprises the preparation or provision of a homogeneous, non-aqueous mixture comprising the amphiphilic polymer composition and at least one active ingredient and / or effect substance.
  • the aqueous active ingredient composition is prepared by first preparing a homogeneous, non-aqueous mixture consisting of amphiphilic polymer composition and active ingredient and / or effect substance and then dispersing the resulting mixture in water or in an aqueous medium.
  • the active compound will generally be incorporated into a liquid form of the amphiphilic polymer composition, for example a melt or, preferably, a solution in an organic solvent. If a solvent is used, the solvent is then as far as possible and preferably completely removed to obtain a solid solution of the active ingredient in the amphiphilic polymer composition.
  • Suitable solvents for this are in principle those which are able to dissolve both the active ingredient and the polymer, for example aliphatic nitriles such as acetonitrile and propionitrile, N, N-dialkylamides of aliphatic carboxylic acids such as dimethylformamide and dimethylacetamide, N-alkyllactams such as N-methylpyrrolidone, the abovementioned aliphatic and alicyclic ethers, for example tetrahydrofuran, halogenated hydrocarbons such as dichloromethane, dichloroethane and mixtures of the abovementioned solvents.
  • aliphatic nitriles such as acetonitrile and propionitrile
  • N, N-dialkylamides of aliphatic carboxylic acids such as dimethylformamide and dimethylacetamide
  • N-alkyllactams such as N-methylpyrrolidone
  • Disperse agent in the amphiphilic polymer composition in an aqueous medium by stirring.
  • the stirring can be carried out at temperatures in the range of the ambient temperature as well as at elevated temperature, for example at a temperature in the range of 10 to 80 ° C and in particular in the range of 20 to 50 ° C.
  • the preparation of the aqueous active ingredient composition is carried out by incorporation of the active ingredient and / or effect substance in an aqueous solution / dispersion of the amphiphilic polymer composition.
  • the procedure is usually such that the incorporation is carried out at a temperature which is above the melting point of the active substance or effect substance and preferably at a temperature at which the active substance or effect substance melt is of low viscosity, ie one Viscosity in the range of 1 to 1000 mPa.s (according to DIN 53019-2 at 25 ° C).
  • the incorporation is carried out using strong shear forces, for example in an Ultraturrax.
  • the preparation of the aqueous active substance composition is carried out by a process comprising the following steps a to c:
  • the solution of the active substance contains the amphiphilic polymer composition and this solution is mixed with water or that the solution of the active ingredient contains only part of the amphiphilic polymer composition or no amphiphilic polymer composition and this solution is mixed with an aqueous solution or dispersion of the amphiphilic polymer composition.
  • the mixing can be carried out in suitable stirred vessels, wherein it is possible to submit both water or the aqueous solution of the amphiphilic polymer composition and for this purpose gives the solution of the active or effect substance, or alternatively presents the solution of the active or effect substance and for this purpose the water or the aqueous Solution of amphiphilic polymer composition gives.
  • the organic solvent e.g. by distillation, optionally adding water.
  • the active substance solution and the water or the aqueous solution of the amphiphilic polymer combination are added. continuously in a mixing zone and this takes continuously from the mixture, from which one then removes the solvent.
  • the mixing zone can be configured as desired. Basically, all apparatuses are suitable for this, which allow a continuous mixing of liquid streams. Such apparatuses are known, for. From Continuous Mixing of Fluids (J.H.Henzler) in Ullmann's Encyclopedia 5th ed. On CD-Rom, Wiley-VCH.
  • the mixing zone may be configured as static or dynamic mixers or mixed forms thereof. In particular, jet mixers or comparable mixers with nozzles are also considered as mixing zones.
  • the mixing zone is the apparatus described in the Handbook of Industrial Crystallization (ASMyerson, 1993 Butterworth-Heinemann, page 139, ISBN 0-7506-9155-7) or a comparable apparatus.
  • the volume ratio of drug solution to water or aqueous solution of the amphiphilic polymer composition can be varied over a wide range and is preferably in the range from 10: 1 to 1:20 and in particular in the range from 5: 1 to 1:10.
  • the solvent should be able to dissolve the amphiphilic polymer composition and the active ingredient in the desired proportions.
  • suitable solvents can be determined by those skilled in the art by routine experimentation.
  • suitable solvents are C 2 -C 4 -alkanols, such as ethanol, n-propanol, n-butanol, isobutanol, the abovementioned aliphatic and alicyclic ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran, ketones, such as Acetone, methyl ethyl ketone.
  • a non-aqueous active ingredient composition is prepared by preparing a homogeneous, non-aqueous mixture of amphiphilic polymer composition and active ingredient and / or effect substance.
  • This composition is usually solid if it contains no liquid ingredients.
  • additives and auxiliaries be incorporated into the composition in a conventional manner.
  • This variant is particularly suitable for the preparation of non-aqueous compositions.
  • the weight ratio of active ingredient and / or effect substance to the amphiphilic polymer composition is in the range from 1:10 to 3: 1 and in particular in the range from 1: 5 to 2: 1.
  • amphiphilic polymer compositions permit the preparation of so-called active agent concentrates containing the active ingredient in an amount of at least 5% by weight, e.g. B. in an amount of 5 to 50 wt .-% and in particular in an amount of 5 to 20 wt .-%, based on the total weight of the composition.
  • compositions according to the invention in particular the aqueous active compound compositions, can be formulated solvent-free or low-solvent, ie. H. the percentage of volatile components in the
  • Active ingredient composition is often not more than 10 wt .-%, in particular Active ingredient composition is often not more than 10% by weight, in particular not more than 5% by weight and especially not more than 1% by weight, based on the total weight of the composition.
  • Volatile constituents are those which have a boiling point below 200 ° C. under atmospheric pressure.
  • compositions of the invention a variety of different active and effect substances can be formulated.
  • a particular embodiment of the invention relates to the formulation of active ingredients for crop protection, d. H. of herbicides, fungicides, nematicides, acaricides, insecticides and plant growth regulators.
  • Nitrophenyl derivatives such as binapacryl, dinocap, dinobutone, nitrophthalic isopropyl; Phenylpyrroles such as fenpiclonil and fludioxonil;
  • Unclassified fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, diciomezine, diciocymet, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin-acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb , Hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalides, toloclofos-methyl, quintozene, zoxamide, isoprothiolane, fluopicolide (picobenzamide); Carpropamide, mandipropamide, N- (2- ⁇ 4- [3- (4-chlorophenyl) -prop-2-ynyl
  • X is CHF or CH 3 ; and R 1 , R 2 are independently halogen, methyl or halomethyl, e.g. CF 3 ; stand;
  • Strobilurins as described in WO 03/075663 by the general formula I for example azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin;
  • Sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid;
  • Cinnamic acid amides and analogs such as dimethomorph, flumetover, flumorp;
  • Amide fungicides such as cyclofenamide and (Z) -N- [ ⁇ - (cyclopropylmethoxyimino) -2,3-difluoro-6- (difluoromethoxy) benzyl] -2-phenylacetamide.
  • 1, 3,4-thiadiazoles such as buthidazole and cyprazole
  • Amides such as allidochlor, benzoylpropyl, bromobutide, chlorthiamide, dimepiperate, dimethenamid, diphenamid, etobenzanide, flampropmethyl, fosamine, isoxaben, metazachlor, monalides, naptalam, pronamide, propanil
  • Aminophosphoric acids such as bilanafos, buminafos, glufosinate-ammonium, glyphosate, sulfosates
  • Aminotriazoles such as amitrole, anilides such as anilofos, mefenacet
  • Aryloxyalkanoic acid such as 2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P, fenoprop, fluroxypyr, MCPA, MCPB, mecoprop, mecoprop-P
  • Oxadiazoles such as methazoles, oxadiargyl, oxadiazon;
  • oxiranes like Tridiphane; Phenols, such as bromoxynil, loxynil;
  • Phenoxyphenoxypropionic acid esters such as clodinafop, cyhalofop-butyl, diclofopmethyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fenthiapropethyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-p-methyl , Isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-p-ethyl, quizalofop-tefuryl; Phenylacetic acids such as chlorfenac; Phenylpropionic acids such as chlorophenprop-methyl; ppi agents such as benzofenap, flumiclorac-pentyl, flumioxazine,
  • Sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron-ethyl, Rimsul - furon, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, tritosulfuron;
  • Cyclohexenone-type pesticides such as alloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim and tralkoxydim.
  • Very particularly preferred cyclohexenone-type herbicidal active compounds are: tepraloxydim (compare AGROW, No.
  • Organo (thio) phosphates such as acephates, azamethiphos, azinphos-methyl, chloropyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorophos, dimethylvinphos, dioxabenzofos, dicrotophos, dimethoates, disulphoton, ethion, EPN, fenitrothion, fenthion, isoxathion , Malathion, Methamidophos, Methidathione, Methyl Parathion, Mevinphos, Monocrotophos, Oxydemeton-methyl, Paraoxone, Parathion, Phenthoate, Phosalone, Phosmet, Phosphamidone, Phorates, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Primiphos-ethyl, Pyraclofos, Pyri - dapendhion,
  • Carbamates such as alanycarb, benfuracarb, bendiocarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, indoxacarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamates; Pyrethroids such as allethrin, bifenthrin, cyfluthrin, cyphenothrin, cycloprothrin, cyperethrin, deltamethrin, esfenvalerate, ethofenprox, fenpropathrin, fenvalate, cyhalothrin, lambda-cyhalothrin, imoprothrin, permethrin, prallethrin, pyherhrin I, pyrethrin II, silafluofen , Tau-flu
  • Arthropod growth regulators a) chitin synthesis inhibitors z.
  • B. benzoylureas such as chlorofluorazuron, cyromacin, diflubenzuron, flucycloxuron, flufenonoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; Buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine;
  • ecdysone antagonists such as halofenozides, methoxyfenozides, tebufenozides;
  • juvenoids such as pyriproxyfen, methoprene, fenoxycarb;
  • lipid biosynthesis inhibitors such as spiroidalofen;
  • Neonicotinoids such as flonicamid, clothianidin, dinotefuran, imidacloprid, thiomethoxam, nitenpyram, nithiazine, acetamiprid, thiacloprid;
  • insecticides such as abamectin, acequinocyl, acetamiprid, a-mitraz, azadirachtin, bensultap, bifenazate, cartap, chlorfenapyr, chlordime form, cyromazine, diafenthiuron, dinetofuran, diofenolan, emamectin, endo- sulfan, ethiprole, fenazaquin, fipronil, formetanate, formetanate hydrochloride, gamma-HCH hydramethylnone, imidacloprid, indoxacarb, isoprocarb, metolcarb, pyridaben, pymetrozine, spinosad, tebufenpyrad, thiamethoxam, thiocyclam, pyridalyl, flonicamid, fluacypyrim, milbemect
  • R -CH 2 O-CH 3 or H
  • R ' -CF 2 CF 2 CF 3 ;
  • R is C 1 -C 4 -alkyl, such as methyl, ethyl, isopropyl or n-butyl, and the compound of the following formula
  • N-phenylsemicarbazones as described in EP-A 462 456 by the general formula I, in particular compounds of the general formula IV
  • R 1 and R 12 are independently hydrogen, halogen, CN, -CC alkyl, -CC 4 alkoxy, d-QrHaloalkyl or CC 4 -haloalkoxy and R 13 is dC ⁇ alkoxy, dC 4 haloalkyl or CC 4 haloalkoxy is, for.
  • B. Compound IV wherein R 11 is 3-CF 3 and R 12 is 4-CN and R 13 is 4-OCF 3 ( metaflumizone).
  • Useful growth regulators are, for example, chlormequat chloride, mepiquat chloride, prohexadione calcium or the group of gibberellins. These include z. Example, the gibberellin GA ⁇ GA 3 , GA 4 , GA 5 and GA 7, etc. and the corresponding exo-16,17-Dihydrogibberelline and the derivatives thereof, for example, the esters with CrC 4 carboxylic acids.
  • Preferred according to the invention is the exo-16,17-dihydro-GA 5 -13-acetate, furthermore
  • a preferred embodiment of the invention relates to the use of the amphiphilic polymer compositions according to the invention for the preparation of aqueous Active substance compositions of fungicides, in particular strobilurins, azoles and 6-aryltriazolo [1, 5a] pyrimidines, as described, for example, in WO 98/46608, WO 99/41255 or WO 03/004465 in each case by the general formula I, in particular for active compounds of the general formula V,
  • R x is a group NR 14 R 15 , or linear or branched C 8 -alkyl which is optionally substituted by halogen, OH, C 1 -C 4 -alkoxy, phenyl or C 3 -C 6 -cycloalkyl, C 2 -C 6- alkenyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, phenyl or naphthyl, where the 4 last mentioned radicals 1, 2, 3 or 4 substituents selected from halogen, OH, -CC 4 alkyl , dC 4 -haloalkoxy, dC -alkoxy and CrC 4 -haloalkyl;
  • R 14, R 5 independently of one another are hydrogen, C 8 alkyl, -C 8 -haloalkyl, C 3 -C ⁇ 0 cycloalkyl, C 3 -C 6 halocycloalkyl, C 2 -C 8 alkenyl, C 4 -C ⁇ 0- alkadienyl, C 2 -C 8 -haloalkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 8 -halocycloalkenyl, C 2 -C 8 -alkynyl, C 2 -C 8 -haloalkynyl or C 3 -C 6 -cycloalkynyl,
  • R 14 and R 15 together with the nitrogen atom to which they are attached, are five- to eight-membered heterocyclyl which is bonded via N and contains one, two or three further heteroatoms from the group O, N and S as ring member and / or one or more substituents from the group halogen, C ⁇ -C6 alkyl, -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C ⁇ -C6 alkoxy, dC 6 haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 haloalkenyloxy, (exo) -C ⁇ -C 6 alkylene and oxy-dC can carry 3 -alkylenoxy; is selected from halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 4
  • L 1 is halogen, dC 6 alkyl or dC 6 haloalkyl and in particular fluorine or chlorine; is halogen, C 1 -C 4 -alkyl, cyano, C 1 -C 4 -alkoxy or CC 4 -haloalkyl and preferably represents halogen or methyl and in particular chlorine.
  • a further preferred embodiment of the invention relates to the use of the amphiphilic polymer compositions according to the invention for preparing active ingredient compositions, in particular aqueous active ingredient compositions of insecticides, in particular arylpyrroles such as chlorfenapyr, of pyrethroids such as bifenthrin, cyfluthrin, cycloprothrin, cypermethrin, deltamethrin, esfen valerates, Etofenprox, fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalothrin, permethrin, silafluofen, tau-fluvalinate, tefluthrin, tralomethrin, alpha-cypermethrin, zeta-cypermethrin and permethrin, of neonicotinoids and of semicarbazones of formula IV.
  • arylpyrroles such as chlor
  • amphiphilic polymer compositions according to the invention are suitable for the preparation of aqueous active substance compositions of pharmaceutical active ingredients and prodrugs.
  • active ingredients and prodrugs include benzodiazepines, antihypertensives, vitamins, cytostatic drugs - especially taxol, anesthetics, neuroleptics, antidepressants, antibiotics, antifungals, fungicides, chemotherapeutics, urologics, antiplatelet agents, sulfa drugs, spasmolytics, hormones, immunoglobulins, sera, thyroid drugs, psychotropic drugs, Parkinson's drugs and others Anti-hyperkinetics, ophthalmics, neuropathy preparations, calcium metabolism regulators, muscle relaxants, anesthetics, lipid-lowering agents, liver therapeutics, coronary agents, cardiacs, immunotherapeutics, regulatory peptides and their inhibitors, hypnotics, sedatives, gynecologics, gout, fibrinolytics, enzyme preparations and transport
  • amphiphilic polymer compositions according to the invention are suitable for the preparation of aqueous preparations of cosmetic active ingredients, especially of cosmetic oils and fats such as peanut oil, jojoba oil, coconut oil, almond oil, olive oil, palm oil, castor oil, soybean oil or wheat germ oil, essential oils such as mountain pine oil, lavender oil, rosemary oil, pine needle oil , Pine oil, eucalyptus oil, peppermint oil, sage oil, bergamot oil, turpentine oil, lemon balm oil, juniper oil, lemon oil, aniseed oil, cardamom oil, camphor oil etc. or for mixtures of these oils.
  • cosmetic oils and fats such as peanut oil, jojoba oil, coconut oil, almond oil, olive oil, palm oil, castor oil, soybean oil or wheat germ oil, essential oils such as mountain pine oil, lavender oil, rosemary oil, pine needle oil , Pine oil, eucalyptus oil, peppermint oil, sage oil, bergamot oil, turpentine oil
  • amphiphilic polymer compositions according to the invention are suitable for the preparation of preparations, in particular of aqueous preparations of food supplements such as water-insoluble vitamins and provitamins such as vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherol derivatives such as tocopherol acetate and vitamin K.
  • Dyes z.
  • the dyes described in DE-A 10245209 and the color Index referred to as a disperse dyes and as solvent dyes compounds, which are also referred to as disperse dyes.
  • a compilation of suitable disperse dyes can be found, for example, in Ulimanns Enzyklopadie der ischen Chemie, 4th Edition, Vol. 10, pp. 155-165 (see also Vol. 7, pp. 585ff - anthraquinone dyes; Vol. 8, pp. 244ff - azo dyes; Vol. 9, p. 313ff - quinophthalone dyes).
  • This reference and the compounds mentioned therein are hereby incorporated by reference.
  • Disperse dyes and solvent dyes which are suitable according to the invention comprise a wide variety of dye classes with different chromophores, for example anthraquinone dyes, monoazo and disazo dyes, quinophthalones, methine and azamethine dyes, naphthalimide dyes, naphthoquinone dyes and nitro dyes.
  • chromophores for example anthraquinone dyes, monoazo and disazo dyes, quinophthalones, methine and azamethine dyes, naphthalimide dyes, naphthoquinone dyes and nitro dyes.
  • disperse dyes which are suitable according to the invention are the disperse dyes of the following color index list: CI Disperse Yellow 1 - 228, CI Disperse Orange 1 - 148, CI Disperse Red 1 - 349, CI Disperse Violet 1 - 97, CI Disperse Blue 1 - 349, CI Disperse Green 1 - 9, CI Disperse Brown 1 - 21, CI Disperse Black 1 - 36.
  • solvent dyes suitable according to the invention are the compounds of the following co-solvents.
  • Dyes which are also suitable according to the invention are derivatives of naphthalene, of anthracene, of perylene, of terylene, of quarterylene and of diketopyrrolopyrrole dyes, perinone dyes, coumarin dyes, isoindoline and isoindolinone dyes, porphyrin dyes, phthalocyanine. and naphthalocyanine dyes; and
  • UV absorbers in particular compounds from groups a to g below
  • the group a) of the 4,4-diarylbutadienes include, for example, compounds of the formula A.
  • the compounds are known from EP-A-916 335.
  • the substituents R 10 and / or Rn are preferably CC 8 -alkyl and C 5 -C 8 -cycloalkyl.
  • the group b) of cinnamic acid esters includes, for example, 2-isoamyl 4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methyl ⁇ -methoxycarbonyl cinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, butyl ⁇ - cyano-.beta.-methyl-p-methoxy-cinnamate and methyl-.alpha.-methoxycarbonyl-p-methoxycinnamate.
  • the group c) of the benzotriazoles includes, for example, 2- (2'-hydroxyphenyl) benzotriazoles, such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl- 2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2 , -hydroxyphenyl) -benzotriazole, 2- (2'-Hydroxy-5 '- (1, 1, 3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 , -methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'- hydroxyphenyl) benzotri
  • Examples of groups d) of hydroxybenzophenones include 2-hydroxybenzophenones, such as 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzo-phenone , 2,2'-dihydroxy-4,4, -dimethoxybenzophenon, 2,2'-dihydroxy-4,4'-dimethoxy benzophenone, 2-hydroxy-4- (2-ethylhexyloxy) benzophenone, 2-hydroxy-4- (n-octyl-oxy) benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-3-carboxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and their
  • the group e) of the diphenylcyanoacrylates includes, for example, ethyl-2-cyano-3,3-diphenylacrylate, which is obtainable, for example, commercially under the name Uvinul® 3035 from BASF AG, Ludwigshafen, 2-ethylhexyl-2-cyano-3, 3-diphenyl acrylate, which is available commercially for example as Uvinul® 3039 from BASF AG, Ludwigshafen, Germany and 1, 3-bis -.
  • the group f) of the oxamides includes, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5 , 5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di- tert-butoxanilide and mixtures of ortho-, para-methoxy-disubstituted oxanilides and mixtures of ortho and para-ethoxy disubstituted oxanilides.
  • Group g) of 2-phenyl-1,3,5-triazines includes, for example, 2- (2-hydroxyphenyl) -1,3,5-triazines such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2,4-dihydroxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl
  • the aqueous active substance compositions according to the invention may also contain conventional surface-active substances and other additives.
  • Surfactants include surfactants, dispersing aids and wetting agents.
  • the other additives include in particular thickeners, defoamers, preservatives, antifreeze stabilizers, etc.
  • anionic, cationic, nonionic and amphoteric surfactants are usable, wherein polymer surfactants and surfactants with heteroatoms are included in the hydrophobic group.
  • the anionic surfactants include, for example, carboxylates, especially alkali, alkaline earth and ammonium salts of fatty acids, eg. B. potassium stearate, which are commonly referred to as soaps; glutamates; Sarcosinates, e.g.
  • the cationic surfactants include, for example, quaternized ammonium compounds, in particular alkyltrimethylammonium and dialkyldimethylammonium halides and alkylsulfates, and also pyridine and imidazoline derivatives, in particular alkylpyridinium halides.
  • Nonionic surfactants include, for example:
  • Fatty alcohol polyoxyethylene esters for example, lauryl alcohol polyoxyethylene ether acetate, alkyl polyoxyethylene and polyoxypropylene ethers, e.g.
  • lauryl alcohol polyoxyethylene ether acetate alkyl polyoxyethylene and polyoxypropylene ethers
  • alkyl polyoxyethylene and polyoxypropylene ethers e.g.
  • alkylaryl alcohol polyoxyethylene ethers e.g.
  • C 4 H 8 and R 20 H, or C 1 -C 12 -alkyl
  • R C 3 -C 30 -alkyl or C 6 -C 30 alkenyl
  • r and s are each independently 0 to 50, both of which can not be 0, such as iso-tridecyl alcohol and oleyl alcohol polyoxyethylene ethers, alkylphenol
  • amphoteric surfactants include, for example, sulfobetaines, carboxybetaines and alkyldimethylamine oxides, e.g. B. tetradecyldimethylamine oxide.
  • Other surfactants which are to be mentioned here by way of example are perfluorosurfactants, silicone surfactants, phospholipids, such as lecithin or chemically modified lecithins, amino acid surfactants, eg. B. N-lauroylglutamate.
  • alkyl chains of the surfactants listed above are linear or branched radicals of usually 8 to 20 carbon atoms.
  • the aqueous active ingredient composition according to the invention contains not more than 10% by weight, preferably not more than 5% by weight and in particular not more than 3% by weight, e.g. 0.01 to 5 wt .-% or 0.1 to 3 wt .-% of conventional surface-active substances, each based on the total amount of active ingredient and polymer composition.
  • the conventional surfactants then preferably make no more than 5% by weight, and more preferably not more than 3% by weight, e.g. 0.01 to 5 wt .-% or 0.1 to 3 wt .-%, based on the total weight of the composition of.
  • the active substance compositions according to the invention are formulated with surface-active substances.
  • the proportion of conventional surface-active substance is often in the range of 0.5 to 30 wt .-%, in particular in the range of 1 to 20 wt .-%, based on the total amount of active ingredient and polymer composition, or in the range of 0, From 2 to 20% by weight and in particular from 0.5 to 15% by weight, based on the total weight of the formulated composition.
  • compositions of the present invention are their low volatile organic content
  • Parrafin oils aromatic hydrocarbons and aromatic hydrocarbon mixtures, eg. Xylenes, Solvesso 100, 150 or 200, and the like, phenols and alkylphenols, e.g. Phenol, hydroquinone, nonylphenol, etc.
  • ketones having more than 4 C atoms such as cyclohexanone, isophorone, isopherone, acetophenone, acetonaphthone, Alcohols having more than 4 C atoms, such as acetylated lanolin alcohol, cetyl alcohol, 1-decanol, 1-heptanol, 1-hexanol, isooctadecanol, isopropyl alcohol, oleyl alcohol, benzyl alcohol, carboxylic esters, eg. B.
  • dialkyl adipate such as adipic acid bis (2-ethylhexyl) ester
  • dialkyl phthalates such as phthalic acid bis (2-ethylhexyl) esters
  • alkyl acetates also branched alkyl groups
  • stearates such as butyl stearate, glycerol
  • citrates such as acetyltributyl citrate, further cetyloctanoate, methyl oleate, Methyl p-hydroxybenzoate, methyl tetradecanoate, propyl p-hydroxybenzoate, methylbenzoate
  • lactic acid esters such as isopropyl lactate, butyl lactate and 2-ethylhexyl lactate
  • vegetable oils such as palm oil, rapeseed oil, castor oil and derivatives thereof such as e.g.
  • Suitable thickeners are compounds which give the formulation a pseudoplastic flow behavior, ie high viscosity at rest and low viscosity in the agitated state.
  • polysaccharides or organic layer minerals such as Xanthan Gum ® (Kelzan ® from. Kelco), Rhodopol ® 23 (Rhone Poulenc) or Veegum ® (from RT Vanderbilt) or Attaclay ® (Engelhardt) to call, said xanthan gum ® is preferably used.
  • silicone emulsions such as, for example, silicone ® SRE, from Wacker, or Rhodorsil ® from Rhodia
  • long-chain alcohols such as, for example, silicone ® SRE, from Wacker, or Rhodorsil ® from Rhodia
  • fatty acids such as, for example, fatty acids, organofluorine compounds and mixtures thereof.
  • Bactericides may be added to stabilize the compositions of the invention against attack by microorganisms.
  • Suitable bactericides are, for example Proxel ® from. ICI or Acetide ® RS from. Thor Chemie and Kathon ® MK from Rohm & Haas.
  • Suitable antifreeze are organic polyols, eg. As ethylene glycol, propylene glycol or glycerol. These are usually used in amounts of not more than 10% by weight, based on the total weight of the active ingredient composition, in order not to exceed the desired content of volatile compounds.
  • the proportion thereof of various volatile organic compounds is preferably not more than 1 wt .-%, in particular not more than 1000 ppm.
  • the active ingredient compositions of the invention may contain 1 to 5 wt .-% buffer based on the total amount of the formulation prepared for pH regulation, wherein the amount and type of buffer used depends on the chemical properties of the active ingredient or the active ingredients.
  • buffers are alkali salts of weak inorganic or organic acids such. For example, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.
  • the active substance or effect substance compositions according to the invention can be used in a manner comparable to conventional formulations of the particular active substance or effect substance.
  • active ingredient compositions containing at least one insecticidal, acaricidal or nematicidal active ingredient can be used to control harmful insects, acarids, or nematodes.
  • active ingredient compositions according to the invention contain at least one fungicidal active ingredient, they can be used to combat harmful fungi.
  • the active compound compositions according to the invention contain a herbicidal active ingredient, they can be used for combating grass weeds and the like.
  • compositions according to the invention are used in particular for protecting plants against attack by harmful organisms such as insects, acarina, nematodes or for protection against infestation with phytopathogenic fungi and the like, or in seed treatment or in material protection, for example for the protection of lignocellulosic materials such as wood, against infestation with noxious insects, such as wood-destroying beetles, termites, ants and the like, or against infestation with wood-discoloring or wood-destroying fungi.
  • harmful organisms such as insects, acarina, nematodes or for protection against infestation with phytopathogenic fungi and the like
  • material protection for example for the protection of lignocellulosic materials such as wood, against infestation with noxious insects, such as wood-destroying beetles, termites, ants and the like, or against infestation with wood-discoloring or wood-destroying fungi.
  • compositions according to the invention can also be used in cosmetics or in medicine or in technical applications.
  • feed 1a consisting of 2109 g of methyl methacrylate and 703 g of styrene
  • feed 1b consisting of 1444 g of tetrahydrofuran, 18.6 g of AIBN and 58.4 g of mercaptoethanol
  • reaction product of biuret of Hexamethy-0 lendiisocyanats with a methyl-terminated polyethylene oxide and stirred the reaction mixture while maintaining the temperature until the NCO content was 0%.
  • the average particle diameter was determined by the method of static light scattering on a diluted sample of the aqueous active ingredient formulation at 20 ° C.
  • the aqueous active compound compositions were stored at 54 ° C. for 2 weeks and at 5 ° C. for 2 weeks. In addition, the active ingredient compositions were frozen and thawed again. Storage stability is given when neither sedimentation nor creaming is observed under these conditions.
  • Solubilization method liquid active ingredients and active ingredient melts: 10 g of active ingredient are stirred into 90 g of an aqueous dispersion of an amphiphilic polymer composition containing 30 g of polymer at a temperature at which the active ingredient is present as a low-viscosity melt. Depending on the viscosity of the polymer solution and the active ingredient melt, the stirring is carried out using a magnetic stirrer or an Ultraturrax. The time required for the solubilization equilibrium depends on the polymer composition and on the active substance and can take a few seconds but also a few hours. The solubilization equilibrium is reached when the active ingredient has distributed uniformly in the mixture and no change in particle size is observed despite further energy input.
  • Phase Inversion Method 10 g of the liquid or solid active ingredient and 30 g of the amphiphilic polymer composition (polymer content> 95% by weight) are dissolved in an organic solvent having a boiling point below 100 ° C (eg tetrahydrofuran). Then, while stirring, water is added and then the organic solvent is removed by distillation. So much water is added that the resulting aqueous formulation is 10% by weight of active ingredient and 30% by weight of polymer.
  • an organic solvent having a boiling point below 100 ° C eg tetrahydrofuran
  • Method of solid solution 0.5 g of the amphiphilic polymer composition (polymer content> 95% by weight) and 0.1 g of the active compound are dissolved in about 20 ml of dimethylformamide. Mamid solved. Thereafter, the solvent is completely removed (eg, on a rotary evaporator) to leave a solid solution of hydrophobic drug and amphiphilic polymer composition. A buffered aqueous solution (100 ml, pH 6.8) is added and the mixture is stirred for 24 hours. After filtration, the solution is analyzed by means of HPLC (UV detector) and the concentration of the active ingredient is determined.
  • HPLC UV detector
  • Nozzle Precipitation A 30% aqueous polymer dispersion is mixed with a 40% active / THF solution via two pumps in a mixing device via a mixing nozzle.
  • the throughput of the polymer dispersion is 12 kg / h
  • the throughput of the THF solution is 3 kg / h
  • so that the total throughput is 15 kg / h.
  • the mixing device is comparable to the apparatus described in "Handbook of Industrial Crystallization" (AS Myerson, 1993 Butterworth-Heinemann, page 139, ISBN 0-7506-9155-7) to give a light yellow milky suspension with 8% active ingredient and 24%.
  • THF and part of the water are removed by distillation to give an aqueous nanoparticulate formulation with 10% active ingredient and 30% polymer.
  • the disperse phase (polymer / drug particle) had a spherical structure and had an average diameter, determined by light scattering, of about 30 nm.
  • Pyraclostrobin was formulated according to general procedure 4.
  • the active ingredient composition obtained was homogeneous, almost visually transparent, stable to sedimentation for at least several months and was diluted with water (both with demineralized water and water at 10 ° dH) without any sedimentation or crystallization of the active ingredient occurring.
  • the active ingredient composition obtained was homogeneous, almost visually transparent, stable to sedimentation for at least several months and was diluted with water (both with demineralized water and water at 10 ° dH) without any sedimentation or crystallization of the active ingredient occurring.
  • the disperse phase (polymer / drug particle) had a spherical structure and had an average diameter, determined by light scattering, of about 30 nm.
  • the active ingredient composition obtained was homogeneous, almost visually transparent, stable to sedimentation for at least several months and was diluted with water (both with demineralized water and water at 10 ° dH) without any sedimentation or crystallization of the active ingredient occurring.
  • aqueous active substance composition from Formulation Example 1 was compared with two commercial formulations of the same active ingredient pyraclostrobin with regard to their activity against Phytophthora infestans on tomatoes in the greenhouse according to the following procedure (preventive test, protective activity):
  • the drug formulations were diluted with tap water to the desired drug concentrations (between 4 and 250 ppm).
  • the application on tomato plants was carried out in a spray booth with 25 ml volume, which corresponds to a practical amount of water of about 500 l / ha.
  • the standard mushroom (Phytophthora infestans) was inoculated 7 days after treatment.
  • the test plants were placed in the greenhouse at 18 to 20 ° C and 90% relative humidity. The assessment was made 5 days after inoculation by determining the percentage of attack of the leaves.
  • Table 2 Phytophthora infestans - infection [%] of tomatoes after five days as a function of the active substance content

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Abstract

The invention relates to amphiphilic polymer compositions, to a method for their production and to their use for producing aqueous active ingredient compositions of water-insoluble active ingredients, in particular active ingredients for crop protection. The amphiphilic polymer compositions are obtained by reacting a) at least one hydrophobic polymer P1, which carries functional groups R1 that are reactive in relation to isocyanate groups and which is composed of ethylenically unsaturated monomers M1, comprising: a1) at least 10 wt. %, (in relation to the total quantity of the monomers M1), of monomers M1a of general formula (I), in which X represents oxygen or an N-R4 group; R1, R2, R3, and R4 are defined as cited in the claims and the description; a2) up to 90 wt. %, (in relation to the total quantity of the monomers M1) of neutral, monoethylenically unsaturated monomers M1b, whose solubility in water at 25 °C is less than 50 g/l and which differ from the monomers M1a; and a3) up to 30 wt. %, (in relation to the total quantity of the monomers M1, of ethylenically unsaturated monomers M1c, which differ from the monomers M1a and M1b, b) at least one hydrophilic polymer P2, which carries functional groups R2 that are reactive in relation to isocyanate groups, c) with at least one compound V, which has a functionality of at least 1.5 in relation to the isocyanate groups.

Description

Amphiphile Polymerzusammensetzungen und ihre VerwendungAmphiphilic polymer compositions and their use
Beschreibungdescription
Die vorliegende Erfindung betrifft amphiphile Polymerzusammensetzungen, ein Verfahren zu ihrer Herstellung sowie deren Verwendung zur Herstellung wässriger Wirkstoffzusammensetzungen von in Wasser nicht löslichen Wirkstoffen, insbesondere von Wirkstoffen für den Pflanzenschutz.The present invention relates to amphiphilic polymer compositions, to a process for their preparation and to their use for the preparation of aqueous active substance compositions of water-insoluble active compounds, in particular active ingredients for crop protection.
Wirkstoffe, d. h. Substanzen, die auch in geringer Konzentration bereits eine physiologische Wirkung entfalten können, werden häufig in Form wässriger Wirkstoffzubereitungen formuliert. So werden beispielsweise im Pflanzenschutz die zur Schädlingsbekämpfung eingesetzten Wirkstoffe, d. h. Insektizide, Fungizide und Herbizide, aber auch Wachstumsregulatoren, häufig als wässrige Konzentrate formuliert und vertrie- ben, welche vor ihrer Anwendung durch Zugabe einer großen Menge Wasser auf die gewünschte Anwendungskonzentration verdünnt werden (so genannte „Spritzbrühe"). Auch für pharmazeutisch und kosmetisch aktive Substanzen sowie für Nahrungsmittelzusätze, z. B. Vitamine, Provitamine etc. haben sich wässrige Wirkstoffzubereitungen bewährt. Gleiches gilt für die Formulierung von Effektstoffen, d.h. niedermolekularen Verbindungen, die bereits bei einer geringen Aufwandmenge eine definierte technische Wirkung entfalten, z. B. Farbstoffe und UV-Stabilisatoren.Active ingredients, d. H. Substances which can already have a physiological effect even in low concentrations are often formulated in the form of aqueous active compound preparations. For example, in plant protection, the active ingredients used for pest control, d. H. Insecticides, fungicides and herbicides, but also growth regulators, often formulated and sold as aqueous concentrates, which are diluted to the desired application concentration by adding a large amount of water before use (so-called "spray mixture") Substances as well as food additives, for example vitamins, provitamins, etc., have proven useful in the formulation of effect substances, ie low molecular weight compounds which already have a defined technical effect at a low application rate, eg dyes and UV stabilizers.
Ein prinzipielles Problem bei wässrigen Wirkstoffzubereitungen ist die in der Regel geringe Wasserlöslichkeit der Wirkstoffe, die häufig weniger als 10 g/l bei 23 °C/1013 mbar beträgt. Wässrige Formulierungen derartiger Wirkstoffe sind daher heterogene Systeme, wobei der Wirkstoff als emulgierte bzw. dispergierte Phase in einer kontinuierlichen wässrigen Phase vorliegt. Zur Stabilisierung dieser an sich metastabilen Systeme werden üblicherweise Emulgatoren oder Dispergier hilfsmittel eingesetzt. Deren stabilisierende Wirkung ist jedoch häufig nicht zufriedenstellend, so dass eine Abscheidung des Wirkstoffs, beispielsweise ein Aufrahmen oder ein Sedimentie- ren des Wirkstoffs auftreten kann, insbesondere wenn die wässrige Formulierung längere Zeit bei erhöhter Temperatur und/oder bei stark wechselnden Temperaturen oder in der Nähe des Gefrierpunkts gelagert wird. Dieses Problem ist insbesondere dann ausgeprägt, wenn der Wirkstoff zur Kristallisation neigt.A principal problem with aqueous active substance preparations is the generally low water solubility of the active ingredients, which is frequently less than 10 g / l at 23 ° C./1013 mbar. Aqueous formulations of such agents are therefore heterogeneous systems wherein the active ingredient is present as an emulsified or dispersed phase in a continuous aqueous phase. To stabilize these intrinsically metastable systems usually emulsifiers or dispersants are used. Their stabilizing effect, however, is often unsatisfactory, so that deposition of the active ingredient, for example creaming or sedimentation of the active ingredient may occur, especially if the aqueous formulation is left for a prolonged period at elevated temperature and / or at strongly changing temperatures or in the vicinity of freezing is stored. This problem is particularly pronounced when the drug tends to crystallize.
Häufig werden auch organische Lösungsmittel zur Herstellung wässriger Formulierungen von in Wasser nicht löslichen Wirkstoffen eingesetzt. So verwendet man häufig mit Wasser mischbare Lösungsmittel als Löslichkeitsvermittler, d.h. zur Erhöhung der Löslichkeit des Wirk- bzw. Effektstoffs in der wässrigen Phase. Mit Wasser nicht mischbare Lösungsmittel wiederum dienen dazu, einen bei Anwendungstemperatur festen Wirkstoff in eine flüssige Phase zu überführen, die man dann leichter emulgieren kann. Im Unterschied zu Suspensionen des festen Wirkstoffs ist in den Emulsionen der Wirkstoff in den Lösungsmitteltröpfchen molekular gelöst und ist daher bei Applikation besser verfügbar und daher wirksamer. Der Einsatz größerer Mengen organischer Lösungsmittel ist jedoch auf Grund der bekannten VOC-Problematik aus arbeitshygienischen Gründen, Umweltaspekten und teilweise auch aus toxikologischen Gründen nicht wünschenswert.Frequently, organic solvents are also used to prepare aqueous formulations of water-insoluble active ingredients. For example, it is common to use water-miscible solvents as solubility promoters, ie to increase the solubility of the active or effect substance in the aqueous phase. Immiscible with water Solvents in turn serve to convert a solid at application temperature active ingredient in a liquid phase, which can then emulsify more easily. In contrast to suspensions of the solid active substance, the active substance in the solvent droplets is molecularly dissolved in the emulsions and is therefore more readily available upon application and therefore more effective. The use of larger amounts of organic solvents, however, is not desirable due to the known VOC problem for occupational hygiene reasons, environmental aspects and sometimes also for toxicological reasons.
Ein weiterer Nachteil konventioneller wässriger Wirkstoffaufbereitungen ist die vergleichsweise große Teilchengröße der in der wässrigen Phase suspendierten bzw. emulgierten Wirkstoffpartikel bzw. Wirkstofftröpfchen, die in der Regel mehrere μm beträgt. Wünschenswert sind jedoch wässrige Formulierungen, in denen der Wirkstoff in möglichst feinverteilter Form vorliegt, um einerseits eine gleichmäßige Verteilung in der Formulierung und damit eine bessere Handhabbarkeit und Dosierbarkeit zu gewährleisten und gleichzeitig, um die Bioverfügbarkeit des Wirkstoffs in der Formulierung zu erhöhen. Erstrebenswert sind dabei Formulierungen, in denen die Wirkstoff- haltige Phase mittlere Teilchengrößen unterhalb 500 nm und insbesondere unterhalb 300 nm aufweist.Another disadvantage of conventional aqueous active substance preparations is the comparatively large particle size of the active ingredient particles or active substance droplets suspended or emulsified in the aqueous phase, which is generally several μm. However, aqueous formulations in which the active ingredient is present in the most finely divided form are desirable in order, on the one hand, to ensure a uniform distribution in the formulation and thus better handling and meterability and, at the same time, to increase the bioavailability of the active ingredient in the formulation. Desirable are formulations in which the active ingredient-containing phase has mean particle sizes below 500 nm and in particular below 300 nm.
Verschiedentlich wurde die Verwendung von amphiphilen Blockcopolymeren zur Solu- bilisierung von in Wasser unlöslichen Wirkstoffen in einem wässrigen Vehikel vorgeschlagen. Der Begriff „Solubilisier ung" bezeichnet eine unter Verwendung von löslich- keitsvermittelnden Substanzen (Hilfsstoffen) erreichte stabile gleichmäßige Verteilung des wasserunlöslichen Wirk- bzw. Effektstoffs in der wässrigen Phase wobei die Partikel der dispersen Wirkstoffphase häufig so klein sind, dass sie sichtbares Licht kaum streuen und die Mischung daher mehr oder weniger transparent erscheint. Die amphiphilen Blockcopolymere weisen dabei in der Regel wenigstens einen hydrophilen Polymerblock und wenigstens einen hydrophoben Polymerblock auf.The use of amphiphilic block copolymers to solubilize water-insoluble drugs in an aqueous vehicle has been proposed on several occasions. The term "solubilization" refers to a stable uniform distribution of the water-insoluble active substance in the aqueous phase achieved using solubility-promoting substances (adjuvants), the particles of the disperse phase of active substance often being so small that they scarcely scatter visible light and the mixture therefore appears to be more or less transparent, the amphiphilic block copolymers generally having at least one hydrophilic polymer block and at least one hydrophobic polymer block.
So schlägt beispielsweise die US 2003/0009004 zu diesem Zweck amphiphile Blockcopolymere vor, die einen hydrophilen Polyethylenimin-Block und einen hydrophoben Block aus einem biologisch abbaubaren, aliphatischen Polyester umfassen. Von Nachteil ist jedoch, dass vergleichsweise große Mengen Polymer, bezogen auf den Wirk- Stoff benötigt werden, um stabile wässrige Wirkstoffzubereitungen zu erhalten.For example, US 2003/0009004 proposes for this purpose amphiphilic block copolymers comprising a hydrophilic polyethylenimine block and a hydrophobic block of biodegradable aliphatic polyester. A disadvantage, however, is that comparatively large amounts of polymer, based on the active ingredient, are required in order to obtain stable aqueous active substance preparations.
Die US 2003/0157170 beschreibt wasserfreie Wirkstoffzusammensetzungen, die ein amphiphilen Diblockcopolymer mit einem Polyester als hydrophobem Bestandteil und ein Additiv enthalten. Die Zusammensetzungen bilden beim Verdünnen mit Wasser wirkstoffhaltige Mizellen. Nachteilig ist auch hier, dass vergleichsweise große Mengen Polymer, bezogen auf den Wirkstoff benötigt werden.US 2003/0157170 describes anhydrous drug compositions containing an amphiphilic diblock copolymer with a polyester as a hydrophobic ingredient and an additive. The compositions form on dilution with water medicated micelles. Another disadvantage here is that comparatively large amounts of polymer, based on the active ingredient, are required.
Die WO 02/82900 beschreibt die Verwendung amphiphiler Blockcopolymere zur Her- Stellung wässriger Suspensionen von wasserunlöslichen Pflanzenschutzwirkstoffen. Die eingesetzten Blockcopolymere sind erhältlich durch „lebende" bzw. „kontrollierte" radikalische Blockcopolymerisation ethylenisch ungesättigter Monomere. Abgesehen davon, dass derartige Verfahren vergleichsweise aufwändig sind, enthalten die wässrigen Wirkstoffformulierungen größere Mengen an wasserlöslichen organischen Lö- sungsmitteln. Außerdem erfordert das Verfahren den Einsatz von toxischen Übergangsmetallkatalysatoren, die im Produkt verbleiben. Außerdem neigen die Blockcopolymere zur Braunfärbung.WO 02/82900 describes the use of amphiphilic block copolymers for preparing aqueous suspensions of water-insoluble crop protection active ingredients. The block copolymers used are obtainable by "living" or "controlled" radical block copolymerization of ethylenically unsaturated monomers. Apart from the fact that such processes are comparatively complicated, the aqueous active substance formulations contain larger amounts of water-soluble organic solvents. In addition, the process requires the use of toxic transition metal catalysts that remain in the product. In addition, the block copolymers tend to brown.
Die US 4,888,389 beschreibt Blockcopolymere, die einen Polyisobutenblock und einen hydrophilen Block, beispielsweise einen Polyetherblock, aufweisen. Eigene Untersuchungen der Anmelderin haben jedoch gezeigt, dass die dort beschriebenen Blockcopolymere zur Herstellung feinteiliger Wirkstoffzubereitungen nicht geeignet sind.US 4,888,389 describes block copolymers which have a polyisobutene block and a hydrophilic block, for example a polyether block. However, own investigations of the applicant have shown that the block copolymers described there are not suitable for the preparation of finely divided active substance preparations.
Zusammenfassend kann gesagt werden, dass trotz der prinzipiellen Vorteile, die amphiphile Blockcopolymere für die Formulierung wasserunlöslicher Wirk- und Effektstoffe in Wasser oder wässrigen Medien haben, die aus dem Stand der Technik bekannten Blockcopolymere nicht vollständig zufriedenstellend sind, sei es, dass ihre Herstellung sehr kompliziert ist, die Stabilität der wässrigen Wirkstoffzubereitungen nicht zufriedenstellend ist, die Aktivität der Wirkstoffe nachteilig beeinflusst wird oder große Mengen an Polymer, bezogen auf den Wirkstoff erforderlich sind, was neben erhöhten Kosten auch bei der Verwendung derartiger Zubereitungen nachteilig auswirken kann.In summary, despite the principal benefits that amphiphilic block copolymers have for formulating water-insoluble active ingredients in water or aqueous media, block copolymers known in the art are not fully satisfactory, their preparation is very complicated is, the stability of the aqueous active compound preparations is unsatisfactory, the activity of the active ingredients is adversely affected or large amounts of polymer, based on the active ingredient are required, which in addition to increased costs may also adversely affect the use of such preparations.
Der vorliegenden Erfindung liegt daher die Aufgabe zu Grunde, Substanzen bereitzu- stellen, die eine effektive Solubilisierung von in Wasser unlöslichen Wirkstoffen in einem wässrigen Medium ermöglichen. Diese Substanzen sollten insbesondere geeignet sein, wässrige Wirkstoffzusammensetzungen von in Wasser unlöslichen Wirkstoffen bereitzustellen, die keinen oder nur einen sehr geringen Gehalt an flüchtigen organischen Substanzen aufweisen. Weiterhin ist eine hohe Stabilität der unter Verwendung dieser Substanzen hergestellten wässrigen Wirkstoffzusammensetzungen im Hinblick auf Entmischungsvorgänge bei langer Lagerung, bei Zusatz von Elektrolyt und beim Verdünnen mit Wasser wünschenswert.The object of the present invention is therefore to provide substances which enable effective solubilization of water-insoluble active ingredients in an aqueous medium. These substances should be particularly suitable for providing aqueous active substance compositions of water-insoluble active ingredients which have no or only a very low content of volatile organic substances. Furthermore, a high stability of the aqueous active substance compositions prepared using these substances with respect to separation processes during long storage, when adding electrolyte and when diluted with water is desirable.
Diese Aufgabe wird überraschenderweise gelöst durch eine Polymerzusammenset- zung, die erhältlich ist durch Umsetzung von a) wenigstens einem hydrophoben Polymer P1 , das gegenüber Isocyanatgruppen reaktive funktionelle Gruppen RP1 trägt und das aus ethylenisch ungesättigten Monomeren M1 aufgebaut ist, umfassend: a1 ) wenigstens 10 Gew.-%, bezogen auf die Gesamtmenge der Monomere M1 , Monomere M1a der allgemeinen Formel IThis object is surprisingly achieved by a polymer composition obtainable by reacting a) at least one hydrophobic polymer P1 which carries isocyanate-reactive functional groups R P1 and which is composed of ethylenically unsaturated monomers M1, comprising: a1) at least 10% by weight, based on the total amount of monomers M1, of monomers M1a of the general Formula I
Figure imgf000006_0001
worin X für Sauerstoff oder eine Gruppe N-R4 steht; R1 Ci-Cio-Alkyl, C5-Cιo-Cycloalkyl, Phenyl oder Phenyl-C C4-alkyl steht; R2 Wasserstoff oder Cι-C4-Alkyl bedeutet; R3 Wasserstoff oder Cι-C4-Alkyl bedeutet; und R4 Wasserstoff oder C C4-Alkyl bedeutet; a2) bis zu 90 Gew.-%, bezogen auf die Gesamtmenge der Monomere M1 , neutrale, monoethylenisch ungesättigte Monomere M1b, deren Wasserlöslichkeit bei 25°C weniger als 50 g/l beträgt und die von den Monomeren M1 a verschieden sind; und a3) bis zu 30 Gew.-%, bezogen auf die Gesamtmenge der Monomere M1 , e- thylenisch ungesättigte Monomeren M1c, die von den Monomeren M1a und M1 verschieden sind,
Figure imgf000006_0001
wherein X is oxygen or a group NR 4 ; R 1 is Ci-Cio-alkyl, C 5 -Cιo-cycloalkyl, phenyl or phenyl-C C 4 alkyl; R 2 is hydrogen or C 1 -C 4 -alkyl; R 3 is hydrogen or C 1 -C 4 -alkyl; and R 4 is hydrogen or CC 4 alkyl; a2) up to 90% by weight, based on the total amount of monomers M1, of neutral, monoethylenically unsaturated monomers M1b whose solubility in water at 25 ° C. is less than 50 g / l and which are different from the monomers M1a; and a3) up to 30% by weight, based on the total amount of the monomers M1, of ethylenically unsaturated monomers M1c which are different from the monomers M1a and M1,
b) wenigstens einem hydrophilen Polymer P2, das gegenüber Isocyanatgruppen reaktive funktionelle Gruppen RP2 trägt,b) at least one hydrophilic polymer P2 carrying isocyanate-reactive functional groups R P2 ,
c) mit wenigstens einer Isocyanatgruppen enthaltenden Verbindung V, die bezüglich der Isocyanatgruppen eine Funktionalität von wenigstens 1 ,5 aufweist.c) having at least one isocyanate group-containing compound V, which has a functionality of at least 1, 5 with respect to the isocyanate groups.
Die Erfindung betrifft somit die hier beschriebenen amphiphilen Polymerzusammenset- zungen sowie das Verfahren zu ihrer Herstellung.The invention thus relates to the amphiphilic polymer compositions described here and to the process for their preparation.
Die erfindungsgemäßen amphiphilen Polymerzusammensetzungen sind in vorteilhafter Weise geeignet, Wirk- und Effektstoffe, die in Wasser schlecht oder nicht löslich sind, in wässriger Phase zu stabilisieren und ermöglichen daher die Herstellung wässriger Formulierungen derartiger Wirk- und Effektstoffe. Im Unterschied zu den im Stand der Technik beschriebenen Blockcopolymere lassen sich mit ihnen große Mengen an Wirkstoff, bezogen auf das Polymer, in der wässrigen Phase solubilisieren. Gegenstand der vorliegenden Erfindung ist daher auch die Verwendung der hier und im Folgenden beschriebenen amphiphilen Polymerzusammensetzungen zur Stabilisierung von Wirkstoffen und/oder Effektstoffen, die in Wasser schlecht oder nicht löslich sind, in einem wässrigen Medium.The amphiphilic polymer compositions according to the invention are advantageously suitable for stabilizing active substances and effect substances which are poorly or not soluble in water in the aqueous phase and therefore permit the preparation of aqueous formulations of such active substances and effect substances. In contrast to the block copolymers described in the prior art, they can be used to solubilize large amounts of active ingredient, based on the polymer, in the aqueous phase. The present invention therefore also relates to the use of the amphiphilic polymer compositions described here and below for stabilizing active substances and / or effect substances which are poorly or not soluble in water in an aqueous medium.
Gegenstand der vorliegenden Erfindung ist daher auch die Verwendung der hier beschriebenen amphiphilen Polymerzusammensetzungen zur Herstellung von Formulierungen von in Wasser unlöslichen oder schlecht löslichen Wirk- und Effektstoffen, die im Folgenden auch als Wirkstoffzusammensetzung bzw. Effektstoff Zusammensetzung bezeichnet werden.. Eine schlechte Löslichkeit bedeutet in diesem Zusammenhang eine Löslichkeit des Wirk- bzw. Effektstoffs in Wasser von unterhalb 10 g/l, häufig unterhalb 5 g/l, insbesondere unterhalb 1 g/l und speziell unterhalb 0,1 g/l bei 25 °C und 1013 mbar.The present invention therefore also relates to the use of the amphiphilic polymer compositions described here for the preparation of formulations of active ingredients or effect substances which are insoluble or sparingly soluble in water and which are also referred to below as active ingredient composition or effect substance composition. A poor solubility in this term means A solubility of the active or effect substance in water of below 10 g / l, often below 5 g / l, in particular below 1 g / l and especially below 0.1 g / l at 25 ° C and 1013 mbar.
Gegenstand der Erfindung sind weiterhin Wirk- bzw. Effektstoffzusammensetzungen, die wenigstens einen in Wasser schlecht- bzw. unlöslichen Wirkstoff und/oder Effektstoff und wenigstens eine amphiphile Polymerzusammensetzung, wie hier und im Folgenden beschrieben, enthalten.The invention furthermore relates to active or effect compositions which comprise at least one active ingredient which is poorly soluble or insoluble in water and / or effect substance and at least one amphiphilic polymer composition, as described here and below.
Die erfindungsgemäßen Wirk- bzw. Effektstoff Zusammensetzungen können fest oder flüssig sein. Eine bevorzugte Ausführungsform derartiger Zusammensetzung betrifft eine, wässrige, d.h. flüssige Wirkstoffzusammensetzung, die ein wässriges Medium als kontinuierliche Phase und wenigstens eine disperse Phase, enthaltend wenigstens einen Wirkstoff und/oder Effektstoff, der in Wasser bei 25 °C/1013 mbar eine Löslichkeit unterhalb 10 g/l aufweist, und wenigstens eine amphiphile Polymerzusammensetzung enthalten.The active substance or effect substance compositions according to the invention can be solid or liquid. A preferred embodiment of such composition relates to an aqueous, i. liquid active ingredient composition comprising an aqueous medium as the continuous phase and at least one disperse phase containing at least one active ingredient and / or effect substance which has a solubility below 10 g / l in water at 25 ° C / 1013 mbar, and at least one amphiphilic polymer composition ,
Die unter Verwendung der erfindungsgemäßen amphiphilen Blockcopolymere herge- stellten wässrigen Wirkstoffzusammensetzungen von in Wasser schlecht- bzw. unlöslichen Wirk- bzw. Effektstoffen umfassen neben einem wässrigen Medium als kontinuierliche Phase wenigstens eine Wirk- bzw. Effektstoff-haltige Phase, in der der Wirkbzw. Effektstoff und die amphiphile Polymerzusammensetzung in Form von Aggregaten aus Wirkstoff bzw. Effektstoff und den Polymerbestandteilen der amphiphilen Po- lymerzusammensetzung vorliegen. Diese Wirk- bzw. Effektstoff-haltige Phase bildet somit eine disperse Phase, die den Wirkstoff bzw. den Effektstoff und wenigstens eine erfindungsgemäße amphiphile Polymerzusammensetzung enthalten. Die disperse Phase ist in diesen Zusammensetzungen äußerst feinteilig, d. h. die Partikel der dispersen Phase weisen Teilchengrößen deutlich unterhalb 1 μm auf. In der Regel be- trägt der mittlere Teilchendurchmesser, wie er durch Lichtstreuung bestimmt werden kann, nicht mehr 500 nm, häufig nicht mehr als 300 nm und liegt häufig im Bereich von 10 bis 300 nm, vorzugsweise im Bereich von 10 bis 250 nm, insbesondere im Bereich von 20 bis 200 nm oder 20 bis 150 nm und besonders bevorzugt im Bereich von 30 bis 100 nm. Grundsätzlich können die Phasenpartikel noch kleinere mittlere Durchmesser bis hinzu einer nahezu molekulardispersen Verteilung mit Teilchengrößen unterhalb der durch Lichtstreuung erfassbaren Grenze aufweisen (z. B. > 10nm).The aqueous active substance compositions prepared using the amphiphilic block copolymers according to the invention of active ingredients which are poorly soluble or insoluble in water comprise, in addition to an aqueous medium as the continuous phase, at least one phase containing effect or effect substance, in which the active substance or active substance phase contains. Effect substance and the amphiphilic polymer composition in the form of aggregates of drug or Effektstoff and the polymer constituents of the amphiphilic polymer lyolyte composition. This active or effect-containing phase thus forms a disperse phase containing the active substance or the effect substance and at least one amphiphilic polymer composition according to the invention. The disperse phase is extremely finely divided in these compositions, ie the particles of the disperse phase have particle sizes well below 1 .mu.m. As a rule, the average particle diameter is that determined by light scattering may not more than 500 nm, often not more than 300 nm and is often in the range of 10 to 300 nm, preferably in the range of 10 to 250 nm, in particular in the range of 20 to 200 nm or 20 to 150 nm, and particularly preferably in Range from 30 to 100 nm. In principle, the phase particles may have even smaller average diameters up to an almost molecular dispersion with particle sizes below the limit detectable by light scattering (eg> 10 nm).
Eine weitere bevorzugte Ausführungsform der Erfindung betrifft eine, nicht-wässrige, in der Regel feste oder halbfeste Wirkstoffzusammensetzung, die wenigstens einen Wirkstoff und/oder Effektstoff, der in Wasser bei 25 °C/1013 mbar eine Löslichkeit unterhalb 10 g/l aufweist, und wenigstens eine amphiphile Polymerzusammensetzung enthalten, und die im wesentlichen kein oder nur geringe Mengen, d. h. < 10 Gew.-% Wasser enthält. Als weitere Bestandteile können diese Zusammensetzungen die für den jeweiligen Anwendungszweck typischen Hilfsmittel und Additive enthalten.A further preferred embodiment of the invention relates to a non-aqueous, generally solid or semi-solid active ingredient composition which has at least one active ingredient and / or effect substance which has a solubility below 10 g / l in water at 25 ° C./1013 mbar, and at least one amphiphilic polymer composition containing substantially no or only minor amounts, d. H. Contains <10 wt .-% water. As further constituents, these compositions may contain the typical auxiliaries and additives for the particular application.
Die erfindungsgemäßen Zusammensetzungen, d.h. sowohl wässrige als auch nicht- wässrige Zusammensetzungen, liefern bei beim Verdünnen wässrige Aufbereitungen des Wirk- bzw. Effektstoffs, umfassend eine wässrige, kontinuierliche Phase und wenigstens eine Wirkstoff- bzw. Effektstoff-haltige Phase mit mittleren Teilchengrößen deutlich unterhalb 1 μm, typischerweise nicht mehr 500 nm, häufig nicht mehr als 300 nm, z. B. im Bereich von 10 bis 300 nm, vorzugsweise im Bereich von 10 bis 250 nm, insbesondere im Bereich von 20 bis 200 nm oder 20 bis 150 nm und besonders bevorzugt im Bereich von 30 bis 100 nm.The compositions of the invention, i. both aqueous and nonaqueous compositions, when diluted, provide aqueous preparations of the effect substance comprising an aqueous, continuous phase and at least one phase containing active substance with average particle sizes well below 1 μm, typically no longer 500 nm, often not more than 300 nm, z. In the range of 10 to 300 nm, preferably in the range of 10 to 250 nm, in particular in the range of 20 to 200 nm or 20 to 150 nm and particularly preferably in the range of 30 to 100 nm.
Die hier angegebenen Teilchengrößen sind gewichtsmittlere Teilchengrößen, wie sie durch dynamische Lichtstreuung ermittelt werden können. Verfahren hierzu sind dem Fachmann geläufig, beispielsweise aus H. Wiese in D. Distler, Wässrige Polymerdispersionen, Wiley-VCH 1999, Kapitel 4.2.1 , S. 40ff und dort zitierte Literatur sowie H. Auweter, D. Hörn, J. Colloid Interf. Sei. 105 (1985) 399, D. Lüge, D. Hörn, Colloid Po- lym. Sei. 269 (1991 ) 704 oder H. Wiese, D. Hörn, J. Chem. Phys. 94 (1991 ) 6429.The particle sizes given here are weight-average particle sizes, as can be determined by dynamic light scattering. Methods for this purpose are familiar to the person skilled in the art, for example from H. Wiese in D. Distler, Aqueous Polymer Dispersions, Wiley-VCH 1999, Chapter 4.2.1, p 40ff and literature cited therein and H. Auweter, D. Horn, J. Colloid Interf , Be. 105 (1985) 399, D. Lie, D. Horn, Colloid Polym. Be. 269 (1991) 704 or H. Wiese, D. Horn, J. Chem. Phys. 94 (1991) 6429.
Die Begriffe „wässriges Medium" und „wässrige Phase" umfassen hier und im Folgenden Wasser, wässrige Mischungen von Wasser mit bis zu 10 Gew.-%, bezogen auf die Mischung, an organischen Lösungsmitteln, die mit Wasser mischbar sind, und Lösun- gen von Feststoffen in Wasser oder in den wässrigen Mischungen. Beispiele für mit Wasser mischbare Lösungsmittel umfassen C3-C -Ketone wie Aceton und Methylethyl- keton, cyclische Ether wie Dioxan und Tetrahydrofuran, Cι-C -Alkanole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, tert.-Butanol, Polyole und deren Mono- und Dimethylether wie Glykol, Propandiol, Ethylenglykolmonomethylether, Diethy- lenglykol, Diethylenglykolmonomethylether, Diethylenglykoldimethylether, Glycerin, weiterhin C2-C3-Nitrile wie Acetonitril und Propionitril, Dimethylsulfoxyd, Dimethylfor- mamid, Formamid, Acetamid, Dimethylacetamid, Butyrolacton, 2-Pyrrolidon und N-Methylpyrrolidon.The terms "aqueous medium" and "aqueous phase" here and below include water, aqueous mixtures of water with up to 10 wt .-%, based on the mixture, of organic solvents which are miscible with water, and solutions of solids in water or in the aqueous mixtures. Examples of water-miscible solvents include C 3 -C ketones, such as acetone and methyl ethyl ketone, cyclic ethers, such as dioxane and tetrahydrofuran, C 1 -C 4 -alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert. Butanol, polyols and their mono- and dimethyl ethers such as glycol, propanediol, ethylene glycol monomethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, glycerol, furthermore C 2 -C 3 -nitriles such as acetonitrile and propionitrile, dimethylsulfoxide, dimethylformamide, formamide, acetamide, dimethylacetamide, butyrolactone, 2-pyrrolidone and N-methylpyrrolidone.
Der Begriff „Funktionalität" steht hier und im Folgenden für die mittlere Anzahl der jeweiligen funktioneilen Gruppen pro Molekül bzw. pro Polymerkette.The term "functionality" here and below stands for the average number of the respective functional groups per molecule or per polymer chain.
Die erfindungsgemäßen wässrigen Wirkstoffzusammensetzungen zeichnen sich durch eine äußerst hohe Stabilität gegenüber Entmischungen auf. Sie können ohne Entmi- schung über einen längeren Zeitraum von mehren Monaten auch bei erhöhterThe aqueous active compound compositions according to the invention are distinguished by extremely high stability against segregation. You can without decongestion over a longer period of several months even at elevated
Temperatur und/oder bei stark wechselnden Temperaturen gelagert werden. Zudem lassen sich konzentriertere Dispersionen auch ohne Probleme mit Wasser verdünnen, ohne dass es zu Entmischungsphänomenen, wie Koagulation, Kristallisation, Flokkulation oder Sedimentation, kommt. Außerdem weisen die Zusammensetzungen eine hohe Toleranz gegenüber Elektrolyten auf. Zudem ist auf Grund der äußerst feinen Verteilung, entsprechend dem sehr niedrigen Teilchendurchmesser der dispersen Phase, die Aktivität der Wirkstoffe im Vergleich zu konventionellen wässrigen Formulierungen erhöht. Ein weiterer Vorteil ist, dass die erfindungsgemäßen wässrigen Wirkstoffzusammensetzungen auch lösungsmittelarm (Gehalt an flüchtigen Lösungsmitteln < 10 Gew.-%, bezogen auf das Gewicht der Wirkstoffzusammensetzung) oder sogar lösungsmittelfrei (Gehalt an flüchtigen Lösungsmitteln < 1 Gew.- %, bezogen auf das Gewicht der Wirkstoffzusammensetzung) formuliert werden können. Die zur Herstellung der erfindungsgemäßen amphiphilen Polymerzusammensetzung eingesetzten hydrophoben Polymere P1 als auch die hydrophilen Polymere P2 weisen gegenüber Isocyanatgruppen reaktive funktionelle Gruppen RP1 bzw. RP2 auf, die unter Bindungsbildung mit der Isocyanatgruppe der Verbindung V reagieren. Beispiele für geeignete funktionelle Gruppen sind Hydroxylgruppen, Mercaptogruppen (SH) und primäre und sekundäre Aminogruppen. Bevorzugte funktionelle Gruppen sind Hydro- xylgruppen, insbesondere an ein aliphatisehes oder eycloaliphatisehes C-Atom gebundene Hydroxylgruppen.Temperature and / or stored at strongly changing temperatures. In addition, more concentrated dispersions can be diluted without problems with water, without causing segregation phenomena, such as coagulation, crystallization, flocculation or sedimentation. In addition, the compositions have a high tolerance to electrolytes. In addition, due to the extremely fine distribution, corresponding to the very low particle diameter of the disperse phase, the activity of the active ingredients is increased compared to conventional aqueous formulations. Another advantage is that the aqueous active substance compositions according to the invention also low in solvents (content of volatile solvents <10 wt .-%, based on the weight of the active ingredient composition) or even solvent-free (content of volatile solvents <1% by weight, based on the weight the active ingredient composition) can be formulated. The hydrophobic polymers P1 used to prepare the amphiphilic polymer composition according to the invention and the hydrophilic polymers P2 have isocyanate-reactive functional groups R P1 and R P2 , respectively, which react with the isocyanate group of the compound V to form bonds. Examples of suitable functional groups are hydroxyl groups, mercapto groups (SH) and primary and secondary amino groups. Preferred functional groups are hydroxyl groups, in particular hydroxyl groups bound to an aliphatic or eycloaliphatic C atom.
Da die Isocyanatgruppen enthaltende Verbindung V im Mittel pro Molekül wenigstens 1 ,5 Isocyanatgruppen aufweist, bilden sich bei der Umsetzung von V mit dem Polyme- ren P1 und dem Polymeren P2 zumindest teilweise Blockcopolymere, welche sowohl wenigstens einen hydrophoben Polymerblock, welcher sich vom hydrophoben Polymeren P1 ableitet, als auch wenigstens einen hydrophilen Polymerblock, welcher sich vom hydrophilen Polymeren P2 ableitet, aufweisen. Im Unterschied zu den amphiphilen Blockcopolymeren des Stands der Technik sind dabei die Blöcke nicht direkt mit- einander, sondern über einen Linker miteinander verknüpft, welcher wenigstens zwei Urethan- und/oder Harnstoffgruppen aufweist. Im Unterschied zu den Blockcopolyme- ren des Stands der Technik weisen die erhaltenen amphiphilen Polymerzusammensetzungen in der Regel noch in untergeordnetem Maße nichtumgesetzte Polymere P1 und/oder P2 sowie symmetrische Umsetzungsprodukte, die entweder ausschließlich von Polymeren P1 abgeleitete Polymerblöcke oder ausschließlich von Polymeren P2 abgeleitete Polymerblöcke aufweisen. Dennoch bleiben die vorteilhaften amphiphilen Eigenschaften der Polymerzusammensetzung gewahrt.Since the isocyanate group-containing compound V has at least 1.5 isocyanate groups per molecule, reaction of V with the polymer P1 and the polymer P2 at least partially forms block copolymers which comprise both at least one hydrophobic polymer block which is different from the hydrophobic polymer P1, as well as having at least one hydrophilic polymer block derived from the hydrophilic polymer P2. In contrast to the amphiphilic block copolymers of the prior art, the blocks are not linked directly to each other, but via a linker, which at least two Has urethane and / or urea groups. In contrast to the block copolymers of the prior art, the amphiphilic polymer compositions obtained generally still to a lesser extent unreacted polymers P1 and / or P2 and symmetrical reaction products having either polymer blocks exclusively derived from polymers P1 or polymer blocks derived exclusively from polymers P2 , Nevertheless, the beneficial amphiphilic properties of the polymer composition are preserved.
Als hydrophobe Polymere P1 kommen grundsätzlich alle aus ethylenisch ungesättigten Monomeren M1 aufgebauten Polymere in Betracht, die zu wenigstens 10 Gew.-%, vorzugsweise zu wenigstens 30 Gew.-%, insbesondere zu wenigstens 50 Gew.-%, besonders bevorzugt zu wenigstens 60 Gew.-%, bezogen auf die Gesamtmenge der Monomere M1 , Monomere M1a einpolymerisiert enthalten und die die geforderte Anzahl an reaktiven Gruppen RP1 aufweisen.Suitable hydrophobic polymers P1 are in principle all polymers made up of ethylenically unsaturated monomers M1, which contain at least 10% by weight, preferably at least 30% by weight, in particular at least 50% by weight, particularly preferably at least 60% by weight .-%, based on the total amount of monomers M1, monomers M1a in copolymerized form and having the required number of reactive groups R P1 .
Bevorzugte Monomere M1a sind solche, worin R3 in Formel I für Wasserstoff steht. R2 steht vorzugsweise für Wasserstoff oder Methyl. X steht vorzugsweise für O, NH, NCH3 oder NC2H5.Preferred monomers M1a are those in which R 3 in formula I is hydrogen. R 2 is preferably hydrogen or methyl. X is preferably O, NH, NCH 3 or NC 2 H 5 .
R1 steht vorzugsweise für Cι-Cιo-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, 2-Butyl, Isobutyl, tert.-Butyl, 1 -Pentyl, 2-Pentyl, Neopentyl, n-Hexyl, 2-Hexyl, n-Octyl, 2-Ethylhexyl, 2-Propylheptyl oder n-Decyl, wobei für R2 = H R insbesondere von Methyl verschieden ist; - C5-Cι0-Cycloalkyl wie Cyclopentyl, Cyclohexyl oder Methylcyclohexyl, oder Phenyl-CrC^alkyl wie Benzyl, 1- oder 2-Phenylethyl, 1-, 2- oder 3-Phenylpropyl. Insbesondere steht R1 für CrCio-Alkyl, wobei für R2 = H R1 insbesondere von Methyl verschieden ist.R 1 is preferably C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, 1-pentyl, 2-pentyl, neopentyl, n-butyl Hexyl, 2-hexyl, n-octyl, 2-ethylhexyl, 2-propylheptyl or n-decyl, wherein for R 2 = HR is especially different from methyl; - C 5 -Cι 0 -cycloalkyl such as cyclopentyl, cyclohexyl or methylcyclohexyl, or phenyl-CrC ^ alkyl such as benzyl, 1- or 2-phenylethyl, 1-, 2- or 3-phenylpropyl. In particular, R 1 is C 1 -C 10 -alkyl, where R 2 = HR 1 is, in particular, different from methyl.
Besonders bevorzugte Monomere M1a sind daher die Ester der Acrylsäure mitParticularly preferred monomers M1a are therefore the esters of acrylic acid with
C2-C10-Alkanolen (= C2-C10-Alkylacrylate) wie Ethylacrylat, n-Butylacrylat, Isobutylacry- lat, tert.-Butylacrylat, n-Hexylacrylat, 2-Ethylhexylacrylat und 3-Propylheptylacrylat, die Ester der Methacrylsäure mit d-Cio-Alkanolen wie Methylmethacrylat, Ethylmethacry- lat, n-Butylmethacrylat, Isobutylmethacrylat, tert.-Butylmethacrylat und n-Hexylmethacrylat. Bevorzugte Monomere M1a sind außerdem die N-(C2-Cιo-Alkyl)amide der Acrylsäure und der Methacrylsäure sowie die N-(Cι-C2-Alkyl)-N-(C2-C10-alkyl)amide der Acrylsäure und der Methacrylsäure, z. B. N-Ethylacrylamid, N,N-Diethylacrylamid, N-Butylacrylamid, N-Methyl-N-propylacrylamid, N-(n-Hexyl)acrylamid, N-(n-Octyl)acrylamid und die ent- sprechenden Methaerylamide. Insbesondere umfassen die Monomere M1a wenigstens 50 Gew.-%, insbesondere wenigstens 70 Gew.-%, bezogen auf die Gesamtmenge der Monomere M1a wenigstens eines Cι-C4-Alkylmethacrylats (R1 = Cι-C4-Alkyl, R2 = CH3 und R3 = H), und hierunter besonders bevorzugt Methylmethacrylat.C 2 -C 10 -alkanols (= C 2 -C 10 -alkyl acrylates) such as ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate and 3-propylheptyl acrylate, the esters of methacrylic acid C 1 -C 10 alkanols such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate and n-hexyl methacrylate. Preferred monomers M1a are also the N- (C 2 -Cιo-alkyl) amides of acrylic acid and methacrylic acid and the N- (-CC 2 alkyl) -N- (C 2 -C 10 alkyl) amides of acrylic acid and the methacrylic acid, z. For example, N-ethylacrylamide, N, N-diethylacrylamide, N-butylacrylamide, N-methyl-N-propylacrylamide, N- (n-hexyl) acrylamide, N- (n-octyl) acrylamide and the corresponding Methaerylamide. In particular, the monomers M1a comprise at least 50% by weight, in particular at least 70% by weight, based on the total amount of monomers M1a of at least one C 1 -C 4 -alkyl methacrylate (R 1 = C 1 -C 4 -alkyl, R 2 = CH 3 and R 3 = H ), and among these, methyl methacrylate is particularly preferred.
Neben den Monomeren M1a kann das hydrophobe Polymer P1 auch von den Monomeren M1 a verschiedene Monomere M1 b in einer Menge bis 90 Gew.-%, vorzugsweise bis 70 Gew.-%, insbesondere bis 50 Gew.-% und besonders bevorzugt bis 40 Gew.- %, bezogen auf die Gesamtmenge der Monomere M1 einpolymerisiert enthalten. Hierbei handelt es sich um monoethylenisch ungesättigte Monomere mit einer Wasserlös- lichkeit < 50 g/l und häufig < 20 g/l bei 25 °C und 1013 mbar. Beispiele für derartige Monomere M1 b sind vinylaromatische Monomere wie Styrol, α-Methylstryrol, Vinyltolu- ol, etc., Olefine mit 2 bis 10 C-Atomen, vorzugsweise α-Olefine mit 3 bis 10 C-Atomen wie Propen, 1 -Buten, 1-Penten, 1 -Hexen, 1-Octen und 1 -Decen, Vinylester ali- phatischer Carbonsäuren wie Vinylacetat, Vinylpropionat, Vinyllaurat, Vinylnonanoat, Vinyldecanoat, Vinyllaurat und Vinylstearat, ungesättigte Nitrile wie Acrylnitril und Me- thacrylnitril, halogenierte Olefine wie Vinylchlorid, Cn-C2o-Alkylester monoethylenisch ungesättigter Monocarbonsäuren mit vorzugsweise 3 bis 6 C-Atomen, z. B. Cn-C^-Alkylacrylate und Cιι-C2o-Alkylmethacrylate wie Laurylacrylat, Laurylmethacry- lat, Isotridecylacrylat, Isotridecylmethacrylat, Stearylacrylat, Stearylmethacrylat, Di-CrC20-Alkylester ethyleniseh ungesättigter Dicarbonsäuren mit vorzugsweise 4 bis 8 C-Atomen, z. B. Di-CrC20-Alkylester der Fumarsäure und der Maleinsäure wie Di- methylfumarat, Dimethylmaleat, Dibutylfumarat und Dibutylmaleat, Glycidylester monoethylenisch ungesättigter Monocarbonsäuren mit vorzugsweise 3 bis 6 C-Atomen, wie Glycidylacrylat und Glycidylmethacrylat. Bevorzugte Monomere M1 b sind vinyl- aromatische Monomere und hierunter insbesondere Styrol. In einer Ausführungsform beträgt der Anteil der Monomere M1 b 1 bis 90 Gew.-%, vorzugsweise 5 bis 70 Gew.- %, insbesondere 7 bis 50 Gew.-% und besonders bevorzugt 10 bis 40 Gew.-%, bezogen auf die Gesamtmenge der Monomere M1. Vorzugsweise beträgt die Gesamtmenge an Monomeren M1a und M1 b wenigstens 80 Gew.-%, insbesondere wenigstens 90 Gew.-% und besonders bevorzugt wenigstens 95 Gew.-% der Monomere M1.In addition to the monomers M1a, the hydrophobic polymer P1 may also comprise monomers M1b other than the monomers M1a in an amount of up to 90% by weight, preferably up to 70% by weight, in particular up to 50% by weight and particularly preferably up to 40% by weight .-%, based on the total amount of monomers M1 in copolymerized form. These are monoethylenically unsaturated monomers having a water solubility <50 g / l and frequently <20 g / l at 25 ° C. and 1013 mbar. Examples of such monomers M1 b are vinylaromatic monomers, such as styrene, α-methylstyrene, vinyltoluene, etc., olefins having 2 to 10 C atoms, preferably α-olefins having 3 to 10 C atoms, such as propene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene, vinyl esters of aliphatic carboxylic acids such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl nonanoate, vinyl decanoate, vinyl laurate and vinyl stearate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, halogenated olefins such as vinyl chloride, Cn-C 2 o-alkyl esters of monoethylenically unsaturated monocarboxylic acids having preferably 3 to 6 C atoms, for. B. Cn-C ^ alkyl acrylates and Cιι-C 2 o-alkyl methacrylates such as lauryl acrylate, lauryl methacrylate, Isotridecylacrylat, Isotridecylmethacrylat, stearyl acrylate, stearyl methacrylate, di-CrC 20 alkyl ethyleniseh unsaturated dicarboxylic acids having preferably 4 to 8 carbon atoms, eg , B. Di-CrC 20 alkyl esters of fumaric acid and maleic acid such as dimethyl fumarate, dimethyl maleate, dibutyl and dibutyl maleate, glycidyl esters of monoethylenically unsaturated monocarboxylic acids having preferably 3 to 6 carbon atoms, such as glycidyl acrylate and glycidyl methacrylate. Preferred monomers M1 b are vinylaromatic monomers and, among these, in particular styrene. In one embodiment, the proportion of the monomers M1 b is 1 to 90% by weight, preferably 5 to 70% by weight, in particular 7 to 50% by weight and particularly preferably 10 to 40% by weight, based on the total amount the monomers M1. The total amount of monomers M1a and M1b is preferably at least 80% by weight, in particular at least 90% by weight and particularly preferably at least 95% by weight of the monomers M1.
Neben den Monomeren M1a und gegebenenfalls M1 b können die Polymere P1 bis zu 30 Gew.-%, häufig nicht mehr als 20 Gew.-%, insbesondere nicht mehr als 10 Gew.-% oder nicht mehr als 5 Gew.-%, bezogen auf die Gesamtmenge der Monomere M1 , ethyleniseh ungesättigte Monomeren M1c, die von den Monomeren M1a und M1b verschieden sind, einpolymerisiert enthalten.In addition to the monomers M1a and optionally M1b, the polymers P1 can be up to 30 wt .-%, often not more than 20 wt .-%, in particular not more than 10 wt .-% or not more than 5 wt .-%, based to the total amount of monomers M1, ethyleniseh unsaturated monomers M1c, which are different from the monomers M1a and M1b, in copolymerized form.
Die Monomere M1c sind vorzugsweise ausgewählt unter neutralen monoethylenisch ungesättigte Monomere M1c.1 , deren Wasserlöslichkeit bei 25 °C wenigstens 50 g/l und insbesondere wenigstens 100 g/l beträgt und monoethylenisch ungesättigten Monomeren M1c.2, die wenigstens eine ionische oder ionisierbare Gruppe tragen.The monomers M1c are preferably selected from neutral monoethylenically unsaturated monomers M1c.1 whose water solubility at 25 ° C. is at least 50 g / l and in particular at least 100 g / l and monoethylenically unsaturated monomers M1c.2 which carry at least one ionic or ionizable group.
Beispiele für Monomere M1c.1 sind die Amide der vorgenannten ethyleniseh ungesät- tigten Carbonsäuren, insbesondere Acrylamid und Methacrylamid, sowieExamples of monomers M1c.1 are the amides of the abovementioned ethylenically unsaturated carboxylic acids, in particular acrylamide and methacrylamide, and
N-Hydroxyalkylamide, insbesondere N-Hydroxymethylamide der vorgenannten ethyleniseh ungesättigten Carbonsäuren, insbesondere N-Methylolacrylamid und N-Methylolmethacrylamid, ethyleniseh ungesättigte Nitrile wie Methacrylnitril und Acryl- nitril, Hydroxyalkylester der vorgenannten α,ß-ethylenisch ungesättigten C3-C8-Monocarbonsäuren und der C4-C8-Dicarbonsäuren, insbesondere Hydroxyethyl- acrylat, Hydroxyethylmethacrylat, 2- und 3-Hydroxypropylacrylat, 2- und 3-Hydroxypropylmethacrylat, Vinyl- und Allylether von Polyethylenglykolen oder von Alkylpolyethylenglykolen, Ester der vorstehend genannten monoethylenisch ungesättigten Mono- und Dicarbonsäuren mit C2-C4-Polyalkylenglykolen, insbesondere die Ester dieser Carbonsäuren, speziell der Acrylsäure oder der Methacrylsäure mit Polyethylenglykol oder Alkyl-Polyethylenglykolen, wobei der (Alkyl)polyethylenglykol- Rest in derartigen Estern und Ethern üblicherweise ein Molekulargewicht im Bereich von 100 bis 3000 aufweist. Zu den Monomeren M1c.1 zählen weiterhin N-Vinylamide wie N-Vinylformamid, N-Vinylpyrrolidon und N-Vinylcaprolactam. Zu den Monomeren M1c.1 zählen weiterhin Harnstoffgruppen tragende Monomere wieN-hydroxyalkylamides, especially N-hydroxymethylamides of the aforementioned ethyleniseh unsaturated carboxylic acids, in particular N-methylolacrylamide and N-methylolmethacrylamide, ethyleniseh unsaturated nitriles such as methacrylonitrile and acrylonitrile, hydroxyalkyl esters of the aforementioned α, ß-ethylenically unsaturated C 3 -C 8 monocarboxylic acids and the C 4 -C 8 -dicarboxylic acids, in particular hydroxyethyl acrylate, hydroxyethyl methacrylate, 2- and 3-hydroxypropyl acrylate, 2- and 3-hydroxypropyl methacrylate, vinyl and allyl ethers of polyethylene glycols or alkylpolyethylene glycols, esters of the abovementioned monoethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 4 -polyalkylene glycols, in particular the esters of these carboxylic acids, especially of acrylic acid or of methacrylic acid with polyethylene glycol or alkyl-polyethylene glycols, where the (alkyl) polyethylene glycol radical in such esters and ethers usually has a molecular weight in the range from 100 to 3000 on has. The monomers M1c.1 also include N-vinylamides such as N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam. Monomers M1c.1 furthermore include monomers carrying urea groups, such as
N-(2-Acrylamidoethyl)-imidazolin-2-on und N-(2-Methacrylamidoethyl)-imidazolin-2-on und Aldehyd- oder Ketogruppen aufweisende Monomere wie 3-(Acrylamido)-3- methylbutan-2-on (Diacetonacrylamid), 3-(Methacrylamido)-3-methylbutan-2-on, 2,4-Dioxapentylacrylat und 2,4-Dioxapentylmethacrylat. Der Anteil der Monomere M1 c.1 wird vorzugsweise nicht mehr als 20 Gew.-%, und insbesondere nicht mehr als 10 Gew.-%, z. B. 0,1 bis 10 und insbesondere 0,5 bis 5 Gew.-%, bezogen auf die Gesamtmenge der Monomere M1 , ausmachen.N- (2-acrylamidoethyl) -imidazolin-2-one and N- (2-methacrylamidoethyl) -imidazolin-2-one and aldehyde- or keto-containing monomers such as 3- (acrylamido) -3-methylbutan-2-one (diacetone acrylamide ), 3- (methacrylamido) -3-methylbutan-2-one, 2,4-dioxapentyl acrylate and 2,4-dioxapentyl methacrylate. The proportion of the monomers M1 c.1 is preferably not more than 20 wt .-%, and in particular not more than 10 wt .-%, z. B. 0.1 to 10 and in particular 0.5 to 5 wt .-%, based on the total amount of the monomers M1 account.
Zu den Monomeren M1c.2 zählen insbesondere monoethylenisch ungesättigte Mono- mere M1c.2s, die wenigstens eine Säuregruppe oder wenigstens eine anionische Gruppen aufweisen, insbesondere Monomere, die eine Sulfonsäuregruppe, eine Phosphonsäuregruppe oder ein oder zwei Carbonsäuregruppen aufweisen, sowie die Salze derartiger Monomere, insbesondere die Alkalimetallsalze, z. B. die Natrium- oder Kaliumsalze sowie die Ammoniumsalze. Hierzu zählen ethyleniseh ungesättigte Sul- fonsäuren, insbesondere Vinylsulfonsäure, 2-Acrylamido-2-methylpropansulfonsäure, 2-Acryloxyethansulfonsäure und 2-Methacryloxyethansulfonsäure, 3-Acryloxy- und 3-Methacryloxypropansulfonsäure, Vinylbenzolsulfonsäure und deren Salze, ethyleniseh ungesättigte Phosphonsäuren, wie Vinylphosphonsäure und Vinylphosphonsäu- redimethylester und deren Salze und α,ß-ethylenisch ungesättigte C3-C8-Mono- und C -C8-Dicarbonsäuren, insbesondere Acrylsäure, Methacrylsäure, Crotonsäure, Mal- einsäure, Fumarsäure und Itaconsäure. Der Anteil der Monomere M1c.2s wird häufig nicht mehr als 20 Gew.-%, z. B. 0,1 bis 20 Gew.-% und insbesondere 0,5 bis 15 Gew.- %, bezogen auf die Gesamtmenge der Monomere M1 , ausmachen. In einer bevorzugten Ausführungsform enthält das Polymer P1 keine oder nicht mehr als 0,1 Gew.-% Monomere M1c.2s einpolymerisiert.The monomers M1c.2 include, in particular, monoethylenically unsaturated monomers M1c.2s which have at least one acid group or at least one anionic group, in particular monomers which have a sulfonic acid group, a phosphonic acid group or one or two carboxylic acid groups, and the salts of such monomers, in particular the alkali metal salts, e.g. As the sodium or potassium salts and ammonium salts. These include ethyleniseh unsaturated sulfonic acids, in particular vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloxyethanesulfonic acid and 2-methacryloxyethanesulfonic acid, 3-acryloxy- and 3-methacryloxypropanesulfonic acid, vinylbenzenesulfonic acid and its salts, ethyleniseh unsaturated phosphonic acids, such as vinylphosphonic acid and vinylphosphonic acid. redimethylester and their salts and α, ß-ethylenically unsaturated C 3 -C 8 monocarboxylic and C -C 8 -dicarboxylic acids, especially acrylic acid, methacrylic acid, crotonic acid, coloring acid, fumaric acid and itaconic acid. The proportion of monomers M1c.2s is often not more than 20 wt .-%, z. B. 0.1 to 20 wt .-% and in particular 0.5 to 15% by weight, based on the total amount of the monomers M1, make up. In a preferred embodiment, the polymer P1 contains in copolymerized form no or not more than 0.1% by weight of monomers M1c.2s.
Zu den Monomeren M1c.2 zählen weiterhin monoethylenisch ungesättigte Monomere M1c.2k, die wenigstens eine kationische Gruppe und/oder wenigstens eine im Wässrigen protonierbare Gruppe aufweisen. Zu den Monomeren M1c.2k zählen insbesondere solche, die eine protonierbare Aminogruppe, eine quartäre Ammoniumgruppe, eine protonierbare Iminogruppe oder eine quaternisierte Iminogruppe aufweisen. Beispiele für Monomere mit einer protonierbaren Iminogruppe sind N-Vinylimidazol und Vinylpy- ridine. Beispiele für Monomere mit einer quaternisierten Iminogruppe sind N-Alkylvinylpyridiniumsalze und N-Alkyl-N'-vinylimidazoliniumsalze wie N-Methyl-N'-vinylimidazoliniumchlorid oder Metosulfat. Unter den Monomeren M1c.2k werden insbesondere die Monomere der allgemeinen Formel II bevorzugtThe monomers M1c.2 furthermore include monoethylenically unsaturated monomers M1c.2k which have at least one cationic group and / or at least one group which can be protonated in the aqueous. The monomers M1c.2k include, in particular, those which have a protonatable amino group, a quaternary ammonium group, a protonatable imino group or a quaternized imino group. Examples of monomers having a protonatable imino group are N-vinylimidazole and vinylpyridine. Examples of monomers having a quaternized imino group are N-alkylvinylpyridinium salts and N-alkyl-N'-vinylimidazolinium salts such as N-methyl-N'-vinylimidazolinium chloride or metosulphate. Among the monomers M1c.2k, in particular the monomers of the general formula II are preferred
Figure imgf000013_0001
Figure imgf000013_0001
worinwherein
R5 Wasserstoff oder Cι-C4-Alkyl, insbesondere Wasserstoff oder Methyl,R 5 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl,
R6, R7 unabhängig voneinander C1-C4-Alkyl, insbesondere Methyl, undR 6 , R 7 are independently C 1 -C 4 -alkyl, in particular methyl, and
R8 Wasserstoff oder Cι-C4-Alkyl, insbesondere Wasserstoff oder Methyl bedeuten,R 8 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl,
Y für Sauerstoff, NH oder NR9 mit R9 = C C4-Alkyl steht,Y is oxygen, NH or NR 9 with R 9 = CC 4 alkyl,
A für C2-C8-Alkylen, z. B. 1 ,2-Ethandiyl, 1 ,2- oder 1 ,3-Propandiyl, 1 ,4-Butandiyl oder 2-Methyl-1 ,2-propandiyl, das gegebenenfalls durch 1 , 2 oder 3 nicht benachbarte Sauerstoffatome unterbrochen ist, steht undA is C 2 -C 8 alkylene, e.g. B. 1, 2-ethanediyl, 1, 2- or 1, 3-propanediyl, 1, 4-butanediyl or 2-methyl-1, 2-propanediyl, which is optionally interrupted by 1, 2 or 3 non-adjacent oxygen atoms is and
Z~ für ein Anionenäquivalent, z. B. für CI", HSO4 ", % SO4 2" oder CH3OSO3 " etc. steht,Z ~ for an anion equivalent, e.g. B. for CI " , HSO 4 " ,% SO 4 2 " or CH 3 OSO 3 " etc.,
und für R8 = H den freien Basen der Monomere der Formel II. Beispiele für derartige Monomere M1c.2k sind 2-(N,N-Dimethylamino)ethylacrylat, 2-(N,N-Dimethylamino)ethylmethacrylat, 2-(N,N-Dimethylamino)ethylacrylamid, 3-(N,N-Dimethylamino)propylacrylamid, 3-(N,N-Dimethylamino)propylmethacrylamid, 2-(N,N-Dimethylamino)ethylmethacrylamid,and for R 8 = H, the free bases of the monomers of the formula II. Examples of such monomers M1c.2k are 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dimethylamino) ethyl acrylamide, 3- (N, N-dimethylamino) propylacrylamide, 3- (N, N-dimethylamino) propylmethacrylamide, 2- (N, N-dimethylamino) ethylmethacrylamide,
2-(N,N,N-Trimethylammonium)ethylacrylat-Chlorid, 2-(N,N,N-Trimethylammonium)ethylmethacrylat-Chlorid, 2-(N,N,N-Trimethylammonium)ethylmethacrylamid-Chlorid, 3-(N,N,N-Trimethylammonium)propylacrylamid-Chlorid, 3-(N,N,N-Trimethylammonium)propylmethacrylamid-Chlorid,2- (N, N, N-trimethyl ammonium) ethyl acrylate chloride, 2- (N, N, N-trimethyl ammonium) ethyl methacrylate chloride, 2- (N, N, N-trimethyl ammonium) ethyl methacrylamide chloride, 3- (N, N) N, N-trimethylammonium) propylacrylamide chloride, 3- (N, N, N-trimethylammonium) propylmethacrylamide chloride,
2-(N,N,N-Trimethylammonium)ethylacrylamid-Chlorid, sowie die entsprechenden Metosulfate und Sulfate. Weitere geeignete Monomere M1c.2k sind Vinylpyridine und Vinylimidazol und deren Quaternisierungsprodukte.2- (N, N, N-trimethylammonium) ethylacrylamide chloride, and the corresponding metosulfates and sulfates. Further suitable monomers M1c.2k are vinylpyridines and vinylimidazole and their quaternization products.
Der Anteil der Monomere M1 c.2k beträgt vorteilhafterweise nicht mehr als 20 Gew.-%, z.B. 0,1 bis 20 Gew.-%, insbesondere 0,5 bis 15 Gew.-%, und speziell 1 bis 10 Gew.- %, bezogen auf die Gesamtmenge der Monomere M1. In einer bevorzugten Ausführungsform enthält das Polymer P1 keine oder nicht mehr als 0,1 Gew.-% Monomere M1c.2k einpolymerisiert.The proportion of the monomers M1 c.2k is advantageously not more than 20% by weight, e.g. 0.1 to 20 wt .-%, in particular 0.5 to 15 wt .-%, and especially 1 to 10% by weight, based on the total amount of the monomers M1. In a preferred embodiment, the polymer P1 contains in copolymerized form no or not more than 0.1% by weight of monomers M1c.2k.
Zu den Monomeren M1c zählen auch Monomere M1c.3, die zwei oder mehrere, nicht konjugierte ethyleniseh ungesättigte Doppelbindungen aufweisen. Der Anteil derartiger Monomere M1c.3 wird in der Regel nicht mehr als 2 Gew.-% und insbesondere nicht mehr als 0,5 Gew.-%, bezogen auf die Gesamtmonomermenge M1 betragen. Beispiele hierfür sind Vinyl- und Allylester monoethylenisch ungesättigter Carbonsäuren wie Allylacrylat und Allylmethacrylat, Di- und Polyacrylate von Di- oder Polyolen wie Ethy- lenglykoldiacrylat, Ethylenglykoldimethacrylat, Butandioldiacrylat, Butandioldimethacry- lat, Hexandioldiacrylat, Hexandioldimethacrylat, Triethylenglykoldiacrylat, Triethylen- glykoltrimethacrylat, Tris(hydroxymethyl)ethantriacrylat und -trimethacrylat, Penta- erythrittriacrylat und -trimethacrylat, ferner die Allyl- und Methallylester von polyfunktio- nellen Carbonsäuren, wie Diallylmaleat, Diallylfumarat, Diallylphthalat. Typische Monomere M1c.3 sind auch Verbindungen, wie Divinylbenzol, Divinylharnstoff, Diallyl- harnstoff, Triallylcyanurat, N,N'-Divinyl- und N,N'-Diallylimidazolidin-2-on, sowie Methy- lenbisacrylamid und Methylenbismethacrylamid.The monomers M1c also include monomers M1c.3, which have two or more non-conjugated ethyleniseh unsaturated double bonds. The proportion of such monomers M1c.3 will generally be not more than 2% by weight and in particular not more than 0.5% by weight, based on the total monomer amount M1. Examples thereof are vinyl and allyl esters of monoethylenically unsaturated carboxylic acids, such as allyl acrylate and allyl methacrylate, di- and polyacrylates of diols or polyols, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol trimethacrylate, tris (hydroxymethyl ) ethane triacrylate and trimethacrylate, pentaerythritol triacrylate and trimethacrylate, and also the allyl and methallyl esters of polyfunctional carboxylic acids, such as diallyl maleate, diallyl fumarate, diallyl phthalate. Typical monomers M1c.3 are also compounds such as divinylbenzene, divinylurea, diallylurea, triallyl cyanurate, N, N'-divinyl and N, N'-diallylimidazolidin-2-one, as well as methylenebisacrylamide and methylenebismethacrylamide.
Erfindungsgemäß tragen die Polymere P1 reaktive funktionelle Gruppen RP1, die mit den Isocyanatgruppen unter Bindungsbildung reagieren. Die mittlere Anzahl derartiger Gruppen pro Polymermolekül (Funktionalität) beträgt in der Regel nicht mehr als zwei und liegt vorzugsweise im Bereich von 0,3 bis 1 ,8, insbesondere im Bereich von 0,5 bis 1 ,5 und speziell im Bereich von 0,6 bis 1 ,4. Die funktionelle Gruppe RP1 kann in der Polymerkette angeordnet sein und befindet sich vorzugsweise am Ende der Polymerkette.According to the invention, the polymers P1 carry reactive functional groups R P1 which react with the isocyanate groups to form bonds. The average number of such groups per polymer molecule (functionality) is generally not more than two and is preferably in the range of 0.3 to 1.8, in particular in the range of 0.5 to 1.5, and especially in the range of 0, 6 to 1, 4. The functional group R P1 can be found in the Polymer chain can be arranged and is preferably at the end of the polymer chain.
Im Hinblick auf die Verwendung der erfindungsgemäßen amphiphilen Polymerzusam- mensetzung zur Formulierung von Wirkstoffen weist das hydrophobe Polymer P1 vorzugsweise ein zahlenmittleres Molekulargewicht im Bereich von 500 bis 20000 Dalton und insbesondere im Bereich von 1500 bis 15000 Dalton auf.With regard to the use of the amphiphilic polymer composition according to the invention for the formulation of active compounds, the hydrophobic polymer P1 preferably has a number-average molecular weight in the range from 500 to 20,000 daltons and in particular in the range from 1500 to 15,000 daltons.
Polymere P1 sind prinzipiell aus dem Stand der Technik bekannt, beispielsweise aus US 5,556,918 und EP-A 742 238. Ihre Herstellung erfolgt in der Regel durch radikalisch initiierte Lösungspolymerisation der Monomere M1 in Gegenwart eines Initiators und gegebenenfalls eines Reglers, mit der Maßgabe, dass der Initiator beim Zerfall einPolymers P1 are known in principle from the prior art, for example from US 5,556,918 and EP-A 742 238. They are generally prepared by free-radically initiated solution polymerization of the monomers M1 in the presence of an initiator and optionally a regulator, with the proviso that the Initiator at disintegration
Hydroxyl-Radikal (OH-Radikal) und/oder der Regler eine OH-Gruppe oder eine NH2-Gruppe enthält. Geeignete Initiatoren sind organische Hydroperoxide wie tert.- Butylhydroperoxid, Tetrahydrofuranhydroperoxid, Cumolhydroperoxid oder 2,2'-Hydroxyl radical (OH radical) and / or the regulator contains an OH group or an NH 2 group. Suitable initiators are organic hydroperoxides such as tert-butyl hydroperoxide, tetrahydrofuran hydroperoxide, cumene hydroperoxide or 2,2'-
Azobis(2-methyl-N-(2-hydroxyethyl)propionamid). Geeignete Regler sind Aminoalkoho- le, Aminophenole und insbesondere Thioalkanole wie 3-Hydroxypropanthiol, 2-Hyroxy- ethyl-3-mercaptopropionsäureester und vor allem 2-Hydroxyethanthiol (Mercapto- ethanol). Sofern ein derartiger Regler eingesetzt wird, kann die Polymerisation auch in Gegenwart eines konventionellen Initiators durchgeführt werden, beispielsweise eines konventionellen Azostarters oder eines organischen Peroxids wie Azobis-(isobutyro- nitril), Di-(tert.-butyl)peroxid, Didecanoylperoxid, Dibenzoylperoxid, Peressigsäure-tert.- butylester oder 2-Methylperpropionsäure-tert.-butylester. Sofern man die Polymerisation in Gegenwart eines der vorgenannten Regler durchführt, wird man den Regler in der Regel in einer Menge von 0,1 bis 5 Gew.-%, häufig 0,2 bis 4 Gew.-% und insbesondere 0,5 bis 3 Gew.-%, bezogen auf die Gesamtmenge der Monomere M1 , einsetzen. Initiatoren werden in der Regel in einer Menge von 0,05 bis 5 Gew.-%, häufig 0,1 bis 4 Gew.-% und besonders bevorzugt in einer Menge von 0,2 bis 3 Gew.-%, bezogen auf die zu polymerisierenden Monomere M1 eingesetzt. Wegen weiterer Details wird insbesondere auf die Seite 3 der EP 742 238 verwiesen, auf deren Offenbarung Bezug genommen wird.Azobis (2-methyl-N- (2-hydroxyethyl) propionamide). Suitable regulators are amino alcohols, aminophenols and, in particular, thioalkanols, such as 3-hydroxypropanethiol, 2-hydroxyethyl-3-mercaptopropionic acid ester and above all 2-hydroxyethanethiol (mercaptoethanol). If such a regulator is used, the polymerization can also be carried out in the presence of a conventional initiator, for example a conventional azo starter or an organic peroxide such as azobis (isobutyronitrile), di (tert-butyl) peroxide, didecanoyl peroxide, dibenzoyl peroxide, Peracetic acid tert-butyl ester or 2-methylperpropionic acid tert-butyl ester. If the polymerization is carried out in the presence of one of the abovementioned regulators, the regulator is generally added in an amount of from 0.1 to 5% by weight, frequently from 0.2 to 4% by weight and in particular from 0.5 to 3 % By weight, based on the total amount of monomers M1. Initiators are usually added in an amount of 0.05 to 5 wt .-%, often 0.1 to 4 wt .-% and particularly preferably in an amount of 0.2 to 3 wt .-%, based on the polymerizing monomers M1 used. For further details, reference is made in particular to page 3 of EP 742 238, to the disclosure of which reference is made.
Hydrophile Polymere P2, die reaktive Gruppen RP2 aufweisen, sind dem Fachmann grundsätzlich bekannt. Hierbei handelt es sich in der Regel um Polymere, die für sich gesehen in Wasser löslich sind. Die Wasserlöslichkeit der Polymere kann durch neutrale hydrophile Gruppen wie Carboxamidgruppen, Ethergruppen, Lactamgruppen, Oxazolidingruppen, durch anionische Gruppen bzw. saure Gruppen, z. B. Carboxy- latgruppen, Sulfonatgruppen oder Phosphatgruppen, durch basische Gruppen, z. B. durch primäre oder sekundäre Aminogruppen, Imidazolgruppen, Pyridingruppen, oder durch kationische Gruppen, beispielsweise quatemisierte Ammoniumgruppen, quater- nisierte Pyridingruppen oder quatemisierte Imidazolgruppen vermittelt werden. Je nach Art der Gruppen unterscheidet man daher zwischen nichtionischen hydrophilen Polymeren P2, anionischen bzw. sauren Polymeren P2 und basischen bzw. kationischen Polymeren P2. Vorzugsweise handelt es sich bei dem Polymeren P2 um ein nichtionisches Polymer, d. h. der Anteil ionischer Gruppen bzw. saurer oder basischer Gruppen beträgt nicht mehr als 0,5 mol/kg Polymer P2 und insbesondere nicht mehr als 0,1 mol/kg Polymer P2.Hydrophilic polymers P2 which have reactive groups R P2 are known in principle to the person skilled in the art. These are usually polymers that are individually soluble in water. The water solubility of the polymers can be controlled by neutral hydrophilic groups such as carboxamide groups, ether groups, lactam groups, oxazolidine groups, by anionic groups or acidic groups, eg. As carboxylate groups, sulfonate groups or phosphate groups, by basic groups, for. Example by primary or secondary amino groups, imidazole groups, pyridine, or cationic groups, for example quaternized ammonium groups, quaternized pyridine groups or quaternized imidazole groups. Depending on the nature of the groups, a distinction is therefore made between nonionic hydrophilic polymers P2, anionic or acidic polymers P2 and basic or cationic polymers P2. Preferably, the polymer P2 is a nonionic polymer, ie the proportion of ionic groups or acidic or basic groups is not more than 0.5 mol / kg of polymer P2 and in particular not more than 0.1 mol / kg of polymer P2.
Beispiele für nichtionische Polymere P2 sind: aliphatische Polyether, die zu wenigstens 50 Gew.-% und insbesondere zu wenigstens 70 Gew.-% aus Ethylenoxid-Einheiten aufgebaut sind,Examples of nonionic polymers P2 are: aliphatic polyethers which are composed of at least 50% by weight and in particular at least 70% by weight of ethylene oxide units,
- Homo- und Copolymere ethyleniseh ungesättigter Monomere, die wenigstens 50 Gew.-%, insbesondere wenigstens 70 Gew.-%, bezogen auf die Gesamtmenge der Monomere M2 wenigstens ein monoethylenisch ungesättigtes hydrophiles Monomer M2a einpolymerisiert enthalten, das eine Wasserlöslichkeit > 50 g/l und insbesondere > 100 g/l bei 25 °C/1013 mbar aufweist. Geeignete Monomere M2a sind die als Monomere M1c.1 genannten Monomere, insbesondere N-Vinyllactame wie N-Vinylpyrrolidon und N-Vinylcaprolactam, die vorgenannten Amide monoethylenisch ungesättiger Monocarbonsäuren wie Methacrylamid, Acrylamid, die vorgenannten Hydroxyalkylester monoethylenisch ungesättigter Monocarbonsäuren wie Hydroxyethylacrylat und Hydroxyethylmethacrylat, Vinyl und Allylester von Polyethylenglykol und von Alkylpolyethylenglykolen sowie die Ester der Acrylsäure und der Methacrylsäure mit Polyethylenglykolen oder Alkylpolyethylenglykolen.Homo- and copolymers of ethyleniseh unsaturated monomers containing at least 50 wt .-%, in particular at least 70 wt .-%, based on the total amount of the monomers M2 at least one monoethylenically unsaturated hydrophilic monomer M2a in copolymerized form, which has a water solubility> 50 g / l and in particular> 100 g / l at 25 ° C / 1013 mbar. Suitable monomers M2a are the monomers M1c.1 mentioned as monomers, in particular N-vinyllactams such as N-vinylpyrrolidone and N-vinylcaprolactam, the aforementioned amides of monoethylenically unsaturated monocarboxylic acids such as methacrylamide, acrylamide, the aforementioned hydroxyalkyl esters of monoethylenically unsaturated monocarboxylic acids such as hydroxyethyl acrylate and hydroxyethyl methacrylate, vinyl and Allyl esters of polyethylene glycol and of alkyl polyethylene glycols and the esters of acrylic acid and methacrylic acid with polyethylene glycols or alkyl polyethylene glycols.
Poly(2-methyloxazoline) und Poly(2-ethyloxazoline), und Poly(α-hydroxycarbonsäure)ester wie Polyglycolid und Polylactid.Poly (2-methyloxazolines) and poly (2-ethyloxazolines), and poly (α-hydroxycarboxylic acid) esters such as polyglycolide and polylactide.
Beispiele für geeignete anionische Polymere P2 sind solche, die wenigstens 30 Gew.- % und vorzugsweise wenigstens 50 Gew.-%, bezogen auf das Gesamtgewicht des Polymeren P2, monoethylenisch ungesättigte Monomere M2b einpolymerisiert enthalten, die eine Säuregruppe, z. B. eine Carboxylgruppe, eine Sulfonsäuregruppe, eine Phosphatgruppe oder eine Phosphonsäuregruppe, tragen. Beispiele für geeignete Monomere M2b sind die im Zusammenhang mit den Polymeren P1 genannten Monomere M1c.2s, z. B. α,ß-ethylenisch ungesättigte Mono- und Dicarbonsäuren wie Acrylsäure, Methacrylsäure, Vinylessigsäure, monoethylenisch ungesättigte Sulfonsäuren wie Vi- nylsulfonat, Methallylsulfonat, Styrolsulfonsäure, 2-Acrylamido-2-methylpropan- sulfonsäure und 2-Acryloxyethylsulfonsäure, ethyleniseh ungesättigte Phosphonsäuren wie Vinylphosphonat, Allylphosphonat, Methallylphosphonat, 2-Acrylamido-2- methylpropanphosphonsäure und 2-Acryloxyethylphosphonat. Neben den vorgenann- ten Monomeren M2b können geeignete anionische Polymere P2 bis zu 50 Gew.-% und insbesondere bis 30 Gew.-% Monomere M1a und M1 b sowie bis zu 70 Gew.-% Monomere M2a einpolymerisiert enthalten.Examples of suitable anionic polymers P2 are those which contain at least 30% by weight and preferably at least 50% by weight, based on the total weight of the polymer P2, of monoethylenically unsaturated monomers M2b in copolymerized form, which contain an acid group, eg. A carboxyl group, a sulfonic acid group, a phosphate group or a phosphonic acid group. Examples of suitable monomers M2b are the monomers M1c.2s mentioned in connection with the polymers P1, z. B. α, ß-ethylenically unsaturated mono- and dicarboxylic acids such as acrylic acid, methacrylic acid, vinylacetic acid, monoethylenically unsaturated sulfonic acids such as nylsulfonate, methallylsulfonate, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and 2-acryloxyethylsulfonic acid, ethyleniseh unsaturated phosphonic acids such as vinylphosphonate, allylphosphonate, methallylphosphonate, 2-acrylamido-2-methylpropanephosphonic acid and 2-acryloxyethylphosphonate. In addition to the abovementioned monomers M2b, suitable anionic polymers P2 may contain, in copolymerized form, up to 50% by weight and in particular up to 30% by weight of monomers M1a and M1b and up to 70% by weight of monomers M2a.
Beispiele für geeignete kationische Polymere P2 sind Homo- und Copolymere der zu- vor genannten monoethylenisch ungesättigten Monomeren M1 c.2k, sowie Copolymere der Monomere M1c.2k mit den monoethylenisch ungesättigten neutralen Monomeren M1c.1.Examples of suitable cationic polymers P2 are homopolymers and copolymers of the aforementioned monoethylenically unsaturated monomers M1 c.2k, and also copolymers of the monomers M1c.2k with the monoethylenically unsaturated neutral monomers M1c.1.
Unter den Polymeren P2 sind insbesondere solche bevorzugt, die bezüglich der funkti- onellen Gruppen RP2 eine Funktionalität F2 im Bereich von 0,5 bis 3 und insbesondere im Bereich von 0,6 bis 2,5 aufweisen.Among the polymers P2, preference is given in particular to those which have a functionality F2 in the range from 0.5 to 3 and in particular in the range from 0.6 to 2.5 with respect to the functional groups R P2 .
Das zahlenmittlere Molekulargewicht der Polymere P2, bestimmt mittels GPC nach üblichen Methoden, liegt vorzugsweise im Bereich von 500 bis 20000 Dalton und ins- besondere im Bereich von 800 bis 15000 Dalton.The number-average molecular weight of the polymers P2, determined by GPC by customary methods, is preferably in the range from 500 to 20,000 daltons and in particular in the range from 800 to 15,000 daltons.
Unter den Polymeren P2 sind insbesondere aliphatische Polyether bevorzugt, die wenigstens 50 Gew.-% und insbesondere wenigstens 70 Gew.-% und besonders bevorzugt wenigstens 90 Gew.-%, bezogen auf ihr Gesamtgewicht, aus Ethylenoxid- Einheiten aufgebaut sind. Daneben können die aliphatischen Polyether Struktureinheiten aufweisen, die sich von C3-C4-Alkylenoxiden ableiten. Die Polyether können auch eine von Wasserstoff verschiedene Endgruppe aufweisen. Besonders bevorzugte Polyether sind insbesondere solche der allgemeinen Formel III Ra-X-(CHRb-CH2-O)p-H (IM)Among the polymers P2, preference is given in particular to aliphatic polyethers which are at least 50% by weight and in particular at least 70% by weight and more preferably at least 90% by weight, based on their total weight, of ethylene oxide units. In addition, the aliphatic polyethers may have structural units derived from C 3 -C 4 -alkylene oxides. The polyethers may also have an end group other than hydrogen. Particularly preferred polyethers are, in particular, those of the general formula III R a -X- (CHR b -CH 2 -O) p -H (IM)
worinwherein
Ra für Wasserstoff, CrC2o-Alkyl oder Benzyl steht, X Sauerstoff oder NH bedeutet,R a is hydrogen, C 1 -C 20 -alkyl or benzyl, X is oxygen or NH,
Rb Wasserstoff oder Methyl bedeutet, wobei wenigstens 50 mol-%, insbesondere wenigstens 70 mol-% und vorzugsweise wenigstens 90 mol-% der Gruppen R2 für Wasserstoff stehen, p eine ganze Zahl bedeutet, deren Mittelwert im Bereich von 10 bis 500, vorzugs- weise 20 bis 250 und insbesondere 25 bis 100 liegt (Zahlenmittel). Geeignete hydrophile Polymere P2 sind dem Fachmann bekannt und größtenteils kommerziell erhältlich, beispielsweise unter den Handelsbezeichnungen Pluriol® und Pluronic® (Polyether der BASF-Aktiengesellschaft), Sokalan®, Kollidon® (Homo- und Copolymere der Monomere M2a, M2b und M1c.2k), oder können durch Routinemethoden hergestellt werden.R b is hydrogen or methyl, where at least 50 mol%, in particular at least 70 mol% and preferably at least 90 mol% of the groups R 2 are hydrogen, p is an integer whose mean value is in the range from 10 to 500, preferably 20 to 250 and in particular 25 to 100 (number average). Suitable hydrophilic polymers P2 are known to the person skilled in the art and are largely commercially available, for example under the trade names Pluriol® and Pluronic® (polyether from BASF Aktiengesellschaft), Sokalan®, Kollidon® (homo- and copolymers of the monomers M2a, M2b and M1c.2k) , or can be made by routine methods.
Der Gesamtanteil der hydrophoben Polymere P1 an der amphiphilen Polymerzusammensetzung, d.h. die Gesamtmenge aus umgesetztem und nicht umgesetztem Poly- mer P1 , beträgt vorzugsweise 9 bis 90 und insbesondere 20 bis 68 Gew.-% des Gesamtgewichts von Polymer P1 , Polymer P2 und Verbindung V.The total amount of hydrophobic polymers P1 on the amphiphilic polymer composition, i. the total amount of reacted and unreacted polymer P1 is preferably from 9 to 90 and in particular from 20 to 68% by weight of the total weight of polymer P1, polymer P2 and compound V.
Der Gesamtanteil der hydrophoben Polymere P2 an der amphiphilen Polymerzusammensetzung, d.h. die Gesamtmenge aus umgesetztem und nicht umgesetztem Poly- mer P2, beträgt vorzugsweise 9 bis 90 und insbesondere 30 bis 78 Gew.-% des Gesamtgewichts von Polymer P1 , Polymer P2 und Verbindung V.The total amount of hydrophobic polymers P2 on the amphiphilic polymer composition, i. the total amount of reacted and unreacted polymer P2 is preferably from 9 to 90 and in particular from 30 to 78% by weight of the total weight of polymer P1, polymer P2 and compound V.
Der Gesamtanteil der Verbindung V an der amphiphilen Polymerzusammensetzung, d.h. die Gesamtmenge eingesetzten Verbindung V, beträgt vorzugsweise 1 bis 20 und insbesondere 2 bis 15 Gew.-% des Gesamtgewichts von Polymer P1 , Polymer P2 und Verbindung V.The total amount of compound V on the amphiphilic polymer composition, i. the total amount of compound V used is preferably from 1 to 20 and in particular from 2 to 15% by weight of the total weight of polymer P1, polymer P2 and compound V.
Das Gewichtsverhältnis von Polymer P1 und P2 in der amphiphilen Polymerzusammensetzung, jeweils gerechnet als die Gesamtmenge der zur Herstellung eingesetzten Polymere, liegt vorzugsweise im Bereich von 1 :10 bis 10:1 und insbesondere im Bereich von 1 :4 bis 2,2:1.The weight ratio of polymer P1 and P2 in the amphiphilic polymer composition, calculated in each case as the total amount of the polymers used for the preparation, is preferably in the range from 1:10 to 10: 1 and in particular in the range from 1: 4 to 2.2: 1.
Geeignete Verbindungen V mit einer Funktionalität bezüglich der Isocyanatgruppen von wenigstens 1 ,5, insbesondere 1 ,5 bis 4,5 und speziell 1 ,8 bis 3,5 umfassen alipha- tische, cycloaliphatische und aromatische Di- und Polyisocyanate sowie die Isocyanu- rate, Allophanate, Urethdione und Biurete von aliphatischen, cycloaliphatischen und aromatischen Diisocyanaten.Suitable compounds V having a functionality with regard to the isocyanate groups of at least 1.5, in particular 1.5 to 4.5 and especially 1.8 to 3.5 include aliphatic, cycloaliphatic and aromatic di- and polyisocyanates and the isocyanurate, Allophanates, urethdiones and biurets of aliphatic, cycloaliphatic and aromatic diisocyanates.
Vorzugsweise weisen die Verbindungen V im Mittel 1 ,8 bis 3,5 Isocyanatgruppen pro Molekül auf. Beispiele für geeignete Verbindungen V sind aromatische Diisocyanate wie Toluol-2,4-diisocyanat, Toluol-2,6-diisocyanate, kommerziell erhältliche Mischungen von Toluol-2,4- und -2,6-diisocyanat (TDI), n-Phenylendiisocyanat, 3,3'-Diphenyl-4,4'-biphenylendiisocyanat, 4,4'-Biphenylendiisocyanat, 4,4'-Diphenylmethandiisocyanat, 3,3'-Dichlor-4,4'-biphenylendiisocyanat, Cumen-2,4-diisocyanat, 1 ,5-Naphthalindiisocyanat, p-Xylylendiisocyanat, p-Phenylendiisocyanat, 4-Methoxy-1 ,3-phenylendiisocyanat, 4-Chlor-1 ,3-phenylendiisocyanat, 4-Ethoxy-1 ,3-phenylendiisocyanat, 2,4-Dimethylen-1 ,3-phenylendiisocyanat, 5,6-Dimethyl-1 ,3-phenylendiisocyanat, 2,4-Diisocyanatodiphenylether, aliphatische Diisocyanate wie Ethylendiisocyanat, Ethylidendiisocyanat, Propylen-1 ,2-diisocyanat, 1 ,6-Hexamethylendiisocyanat,Preferably, the compounds V have on average from 1.8 to 3.5 isocyanate groups per molecule. Examples of suitable compounds V are aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanates, commercially available mixtures of toluene-2,4- and 2,6-diisocyanate (TDI), n-phenylene diisocyanate, 3,3'-diphenyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, cumene 2,4-diisocyanate, 1, 5-naphthalene diisocyanate, p-xylylene diisocyanate, p-phenylene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-chloro-1, 3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4-dimethylene-1,3-phenylene diisocyanate, 5,6- Dimethyl 1,3-phenylene diisocyanate, 2,4-diisocyanato diphenyl ether, aliphatic diisocyanates such as ethylene diisocyanate, ethylidene diisocyanate, propylene 1,2-diisocyanate, 1,6-hexamethylene diisocyanate,
1 ,4-Tetramethylendiisocyanat, 1 ,10-Decamethylendiisocyanat und cycloaliphatische Diisocyanate, wie Isophorondiisocyanat (IPDI), Cyclohexylen-1 ,2-diisocyanat, Cyclohe- xylen-1 ,4-diisocyanat und Bis(4,4'-lsocyanatocyclohexyl)methan. Unter den Diisocya- naten sind solche bevorzugt, deren Isocyanatgruppen sich in ihrer Reaktivität unter- scheiden, wie Toluol-2,4-diisocyanat, Toluol-2,6-diisocyanat, deren Mischungen und eis- und trans-lsophorondiisocyanat.1, 4-tetramethylene diisocyanate, 1, 10-decamethylene diisocyanate and cycloaliphatic diisocyanates, such as isophorone diisocyanate (IPDI), cyclohexylene-1, 2-diisocyanate, cyclohexyl-1, 4-diisocyanate and bis (4,4'-isocyanatocyclohexyl) methane. Among the diisocyanates, preference is given to those whose isocyanate groups differ in their reactivity, such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, mixtures thereof and cis and trans isophorone diisocyanate.
In einer anderen bevorzugten Ausführungsform der Erfindung setzt man zur Herstellung der erfindungsgemäßen amphiphilen Polymerzusammensetzung ein Biuret oder ein Isocyanurat einer aliphatischen oder cycloaliphatischen Diisocyanatverbindung ein, beispielsweise das Cyanurat von Tetramethylendiisocyanat oder von Hexamethylendii- soeyanat.In another preferred embodiment of the invention, a biuret or an isocyanurate of an aliphatic or cycloaliphatic diisocyanate compound, for example the cyanurate of tetramethylene diisocyanate or of hexamethylene diisocyanate, is used to prepare the amphiphilic polymer composition according to the invention.
Zur Herstellung der erfindungsgemäßen amphiphilen Polymerzusammensetzung setzt man das hydrophobe Polymer P1 und das hydrophile Polymer P2 sukzessive oder gleichzeitig unter Reaktionsbedingungen mit der Verbindung V um, unter denen die Gruppen RP1 bzw. RP2 mit den Isocyanatgruppen unter Bindungsbildung reagieren.To prepare the amphiphilic polymer composition according to the invention, the hydrophobic polymer P1 and the hydrophilic polymer P2 are reacted successively or simultaneously under reaction conditions with the compound V, under which the groups R P1 and R P2 react with the isocyanate groups to form bonds.
Die Umsetzung kann in Abwesenheit oder in Gegenwart geringer Mengen hierfür übli- eher Katalysatoren, welche die Bildung von Urethanen bzw. Harnstoffen fördern, erfolgen. Geeignete Katalysatoren sind beispielsweise tertiäre Amine, z. B. Triethylamin, Tri-n-propylamin, N-Methylpyrrolidin, N-Methylpiperidin und Diazabicyclooctan (DABCO), zinnorganische Verbindungen, insbesondere Dialkylzinn(IV)salze von aliphatischen Carbonsäuren wie Dibutylzinndilaurat und Dibutylzinndioctoat, Zinn(ll)dialkanoate wie Zinndioctoat, sowie Cäsiumsalze wie Cäsiumacetat. Sofern erwünscht, wird man den Katalysator in einer Menge von nicht mehr als 0,1 Gew.-%, bezogen auf die Verbindung V, z. B. in einer Menge von 0,01 bis 0,1 Gew.-%, insbesondere bis 0,05 Gew.-% einsetzen.The reaction may be carried out in the absence or in the presence of small amounts thereof, more preferably catalysts which promote the formation of urethanes or ureas. Suitable catalysts are, for example, tertiary amines, for. As triethylamine, tri-n-propylamine, N-methylpyrrolidine, N-methylpiperidine and diazabicyclooctane (DABCO), organotin compounds, especially dialkyltin (IV) salts of aliphatic carboxylic acids such as dibutyltin dilaurate and dibutyltin dioctoate, tin (II) dialkanoate such as tin dioctoate, and cesium salts like cesium acetate. If desired, the catalyst is added in an amount of not more than 0.1% by weight, based on the compound V, e.g. B. in an amount of 0.01 to 0.1 wt .-%, in particular up to 0.05 wt .-% use.
Die erforderlichen Reaktionstemperaturen hängen naturgemäß von der Reaktivität der funktionellen Gruppe RP1 bzw. RP2 sowie der Isocyanatverbindung V und, sofern eingesetzt, von Art und Menge des verwendeten Katalysators ab. Sie liegt in der Regel im Bereich von 10 bis 120 °C und insbesondere im Bereich von 15 bis 85 °C. Es versteht sich von selbst, dass die Umsetzung der Polymere P1 und P2 mit der Iso- cyanatverbindung V in Abwesenheit von Feuchtigkeit (Wassergehalt vorzugsweise < 10000 ppm und insbesondere < 2000 ppm) erfolgt.The required reaction temperatures are naturally dependent on the reactivity of the functional group R P1 or R P2 and the isocyanate compound V and, if used, on the type and amount of catalyst used. It is usually in the range of 10 to 120 ° C and in particular in the range of 15 to 85 ° C. It goes without saying that the reaction of the polymers P1 and P2 with the isocyanate compound V takes place in the absence of moisture (water content of preferably <10000 ppm and in particular <2000 ppm).
Die Umsetzung kann in Substanz oder in einem organischen Lösungsmittel durchgeführt werden, das gegenüber den Isocyanatgruppen der Verbindung V inert ist. Beispiele für geeignete Lösungsmittel sind aliphatische Ketone wie Aceton, Methylethylketon, Cyclohexanon, Alkylester aliphatischer Carbonsäuren wie Methylacetat, Ethylacetat, Methylpropionat, Ethylpropionat, n-Butylacetat, alicyclische und cyclische Ether wie Diethylether, Diisopropylether, Methyl-tert.-butylether,The reaction can be carried out in bulk or in an organic solvent which is inert to the isocyanate groups of the compound V. Examples of suitable solvents are aliphatic ketones such as acetone, methyl ethyl ketone, cyclohexanone, alkyl esters of aliphatic carboxylic acids such as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-butyl acetate, alicyclic and cyclic ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether,
Tetrahydrofuran, aromatische, aliphatische und alicyclische Kohlenwasserstoffe wie Toluol, Xylole, Hexan, Cyclohexan, sowie N-Alkyllactame wie N-Methylpyrrolidon und Mischungen dieser Lösungsmittel.Tetrahydrofuran, aromatic, aliphatic and alicyclic hydrocarbons such as toluene, xylenes, hexane, cyclohexane, and N-alkyl lactams such as N-methylpyrrolidone and mixtures of these solvents.
Die Umsetzung des Polymers P1 und des Polymers P2 mit der Verbindung V kann sukzessive oder gleichzeitig erfolgen, d. h. Polymer P1 und P2 können nacheinander oder gleichzeitig mit der Verbindung V umgesetzt werden.The reaction of the polymer P1 and the polymer P2 with the compound V can be carried out successively or simultaneously, i. H. Polymer P1 and P2 can be reacted sequentially or simultaneously with the compound V.
Sofern man die Polymere P1 und P2 nacheinander mit der Verbindung V umsetzt, kann man sowohl zunächst das Polymer P1 mit der Verbindung V und anschließend das Polymer P2 mit der Verbindung V umsetzen als auch umgekehrt vorgehen.If the polymers P1 and P2 are reacted successively with the compound V, both the polymer P1 with the compound V and then the polymer P2 with the compound V can be reacted first and vice versa.
Sofern man die Polymere P1 und P2 sukzessive mit der Verbindung V umsetzt, führt man die Umsetzung vorzugsweise so durch, dass nach beendeter Umsetzung mit dem ersten Polymer P1 oder P2 wenigstens 10 mol-% bis 90 mol-%, insbesondere 20 mol- % bis 80 mol-% der Isocyanatgruppen in V mit den funktionellen Gruppen R1 bzw. R2 reagiert haben und 10 bis 90 mol-%, insbesondere 20 bis 80 mol-% der vorhandenen Isocyanatgruppen noch vorliegen. Anschließend führt man dann die Umsetzung mit dem zweiten Polymeren P1 oder P2 durch. Vorzugsweise setzt man daher das erste Polymer P1 oder P2 in einer Menge ein, dass das Molverhältnis von reaktiven Gruppen RP1 bzw. RP2 zur Anzahl der Isocyanatgruppen pro Molekül V im Bereich von 0,1 :1 bis 0,9:1 und insbesondere im Bereich von 0,2:1 bis 0,8:1 liegt. Anschließend setzt man das so erhaltene Produkt mit dem zweiten Polymer ein, wobei man vorzugsweise das zweite Polymer P1 oder P2 in einer solchen Menge einsetzen wird, dass die Gesamt- menge an reaktiven Gruppen RP1 + RP2 wenigstens der Anzahl der Isocyanatgruppen der Verbindung V entspricht. Bevorzugt wird das Verhältnis RP1 + RP2 zur Gesamtmenge an Isocyanatgruppen einen Wert von 1 ,2:1 nicht überschreiten.If the polymers P1 and P2 are reacted successively with the compound V, the reaction is preferably carried out in such a way that after completion of the reaction with the first polymer P1 or P2 at least 10 mol% to 90 mol%, in particular 20 mol% to 80 mol% of the isocyanate groups in V have reacted with the functional groups R 1 or R 2 and 10 to 90 mol%, in particular 20 to 80 mol% of the isocyanate groups present are still present. Subsequently, the reaction is then carried out with the second polymer P1 or P2. Preferably, therefore, the first polymer P1 or P2 is used in an amount such that the molar ratio of reactive groups R P1 or R P2 to the number of isocyanate groups per molecule V is in the range from 0.1: 1 to 0.9: 1 and in particular in the range of 0.2: 1 to 0.8: 1. The product thus obtained is then reacted with the second polymer, the second polymer P1 or P2 preferably being used in an amount such that the total amount of reactive groups R P1 + R P2 is at least equal to the number of isocyanate groups of compound V equivalent. Preferably, the ratio R P1 + R P2 to the total amount of isocyanate groups will not exceed a value of 1.2: 1.
Sofern man die Polymere P1 und P2 gleichzeitig mit der Isocyanatverbindung V um- setzt, wird man vorzugsweise die Polymere P1 und P2 in einer Menge einsetzen, dass das Molverhältnis von reaktiven Gruppen RP1 + RP2 zu den Isocyanatgruppen wenigstens 1 :1 beträgt. Bevorzugt wird das Verhältnis RP1 + RP2 zur Gesamtmenge an Isocyanatgruppen einen Wert von 1 ,2:1 nicht überschreiten.If the polymers P1 and P2 are reacted simultaneously with the isocyanate compound V, it is preferable to use the polymers P1 and P2 in an amount such that the molar ratio of reactive groups R P1 + R P2 to the isocyanate groups is at least 1: 1. Preferably, the ratio R P1 + R P2 to the total amount of isocyanate groups will not exceed a value of 1.2: 1.
Die Isocyanatverbindung V kann in der Umsetzung als solche eingesetzt werden. Es ist jedoch auch möglich, die Isocyanatverbindung V in einer Form einzusetzen, bei der ein Teil der Isocyanatgruppen durch eine Schutzgruppe reversibel blockiert ist. Verbindungen, die Isocyanatgruppen blockieren (verkappen oder schützen), sind in der Literatur vielfach beschrieben (vgl. z. B. Z. W. Wicks, Prog. Org. Coat. 3(1975) 73-99 sowie 9(1981 ) 3-28 oder Houben-Weyl, Methoden der Organischen Chemie Bd. XI V/2, S. 61 ff., Georg Thieme Verlag, Stuttgart 1963). Als Blockierungsmittel von Isocyanatgruppen seien beispielhaft Phenole, Caprolactam, Imidazole, Pyrazole, Pyrazolinone, 1 ,2,4-Triazole, Diketopiperazine, Malonsäureester und Oxime genannt. Zur Erzielung des erfindungsgemäßen Erfolgs ist der Einsatz von partiell reversibel blockierten Iso- cyanaten jedoch nicht erforderlich.The isocyanate compound V can be used as such in the reaction. However, it is also possible to use the isocyanate compound V in a form in which a part of the isocyanate groups is reversibly blocked by a protective group. Compounds which block (cap or protect) isocyanate groups have been described many times in the literature (see, for example, BZW Wicks, Prog. Org. Coat 3 (1975) 73-99 and 9 (1981) 3-28 or Houben-Weyl , Methods of Organic Chemistry Bd. XI V / 2, p. 61 ff., Georg Thieme Verlag, Stuttgart 1963). Examples of blocking agents of isocyanate groups include phenols, caprolactam, imidazoles, pyrazoles, pyrazolinones, 1,2,4-triazoles, diketopiperazines, malonic esters and oximes. To achieve the success of the invention, however, the use of partially reversibly blocked isocyanates is not required.
In einer besonders bevorzugten Ausführungsform der Erfindung stellt man in einem ersten Reaktionsschritt das hydrophobe Polymer P1 durch radikalische Lösungsmittelpolymerisation in der oben beschriebenen Weise her und führt in der so erhaltenen flüssigen Reaktionsmischung die Umsetzung mit dem Isocyanat V in der hier beschriebenen Weise durch, ohne das Polymer P1 zuvor zu isolieren. Anschließend setzt man dann die erhaltene Reaktionsmischung mit dem Polymeren P2, vorzugsweise einem Polyether, um. Alternativ kann man die Gewünschte Menge an Polymer P2 zu dem so hergestellten Polymeren P1 geben und anschließend die Umsetzung mit der Verbin- düng V durchführen.In a particularly preferred embodiment of the invention, in a first reaction step, the hydrophobic polymer P1 is prepared by free-radical solvent polymerization in the manner described above and carries out the reaction with the isocyanate V in the liquid reaction mixture thus obtained, without the polymer Isolate P1 in advance. The reaction mixture obtained is then reacted with the polymer P2, preferably a polyether. Alternatively, the desired amount of polymer P2 can be added to the polymer P1 thus prepared and then the reaction with the compound V can be carried out.
Für die Herstellung der wässrigen Wirkstoffformulierungen kann die erfindungsgemäß erhaltene Polymerzusammensetzung aus der Reaktionsmischung isoliert werden. Es ist jedoch auch möglich, die Reaktionsmischung als solche einzusetzen.For the preparation of the aqueous active ingredient formulations, the polymer composition obtained according to the invention can be isolated from the reaction mixture. However, it is also possible to use the reaction mixture as such.
In einer bevorzugten Ausführungsform der Erfindung ersetzt man das zur Herstellung der Polymerzusammensetzung eingesetzte Lösungsmittel teilweise oder vollständig durch Wasser, wodurch man eine wässrige Dispersion der amphiphilen Polymerzusammensetzung erhält. Dies kann beispielsweise dadurch bewirkt werden, dass man das Lösungsmittel zunächst abdestilliert und anschließend den Rückstand in Wasser oder einem wässrigen Medium dispergiert. Auch kann man zu der Lösung der Polymerzusammensetzung Wasser geben und das Lösungsmittel im Anschluss an die Zugabe des Wassers oder parallel hierzu entfernen. Die Herstellung der erfindungsgemäßen Wirkstoff- bzw. Effektstoffzusammensetzung kann in unterschiedlicher Weise erfolgen. Typischerweise umfasst die Herstellung der erfindungsgemäßen Wirkstoff- bzw. Effektstoffzusammensetzung die Herstellung bzw. Bereitstellung einer homogenen, nichtwässrigen Mischung, umfassend die amphiphile Polymerzusammensetzung und wenigstens einen Wirkstoff und/oder Effektstoff.In a preferred embodiment of the invention, the solvent used to prepare the polymer composition is partially or completely replaced by water to give an aqueous dispersion of the amphiphilic polymer composition. This can be effected, for example, by first distilling off the solvent and then dispersing the residue in water or in an aqueous medium. Also, one may add water to the solution of the polymer composition and remove the solvent following or in parallel with the addition of the water. The preparation of the active ingredient or effect substance composition according to the invention can take place in different ways. Typically, the preparation of the active ingredient composition according to the invention comprises the preparation or provision of a homogeneous, non-aqueous mixture comprising the amphiphilic polymer composition and at least one active ingredient and / or effect substance.
In einer ersten Ausführungsform der vorliegenden Erfindung stellt man die wässrige Wirkstoffzusammensetzung her, indem man zunächst eine homogene, nicht wässrige Mischung, bestehend aus amphiphiler Polymerzusammensetzung und Wirkstoff und/oder Effektstoff herstellt und die so erhaltene Mischung anschließend in Wasser oder einem wässrigen Medium dispergiert. Zum Herstellen der homogenen, nicht wässrigen Mischung wird man in der Regel den Wirkstoff in eine flüssige Form der amphiphilen Polymerzusammensetzung, beispielsweise eine Schmelze oder vorzugsweise eine Lösung in einem organischen Lösungsmittel einarbeiten. Sofern man ein Lösungsmittel verwendet, wird man anschließend das Lösungsmittel möglichst weitgehend und vorzugsweise vollständig entfernen, wobei man eine feste Lösung des Wirkstoffs in der amphiphilen Polymerzusammensetzung erhält. Geeignete Lösungsmittel hierfür sind grundsätzlich solche, die sowohl den Wirkstoff als auch das Polymer zu lösen vermögen, beispielsweise aliphatische Nitrile wie Acetonitril und Propionitril, N,N-Dialkylamide aliphatischer Carbonsäuren wie Dimethylformamid und Dimethylacetamid, N-Alkyllactame wie N-Methylpyrrolidon, die vorgenannten aliphatischen und alicyclischen Ether, beispielsweise Tetrahydrofuran, halogenierte Kohlenwasserstoffe wie Dichlormethan, Dichlorethan und Mischungen der vorgenannten Lösungsmittel. Zur Herstellung der erfindungsgemäßen wässrigen Zusammensetzung wird man anschließend die so erhaltene feste Lösung desIn a first embodiment of the present invention, the aqueous active ingredient composition is prepared by first preparing a homogeneous, non-aqueous mixture consisting of amphiphilic polymer composition and active ingredient and / or effect substance and then dispersing the resulting mixture in water or in an aqueous medium. In order to prepare the homogeneous, non-aqueous mixture, the active compound will generally be incorporated into a liquid form of the amphiphilic polymer composition, for example a melt or, preferably, a solution in an organic solvent. If a solvent is used, the solvent is then as far as possible and preferably completely removed to obtain a solid solution of the active ingredient in the amphiphilic polymer composition. Suitable solvents for this are in principle those which are able to dissolve both the active ingredient and the polymer, for example aliphatic nitriles such as acetonitrile and propionitrile, N, N-dialkylamides of aliphatic carboxylic acids such as dimethylformamide and dimethylacetamide, N-alkyllactams such as N-methylpyrrolidone, the abovementioned aliphatic and alicyclic ethers, for example tetrahydrofuran, halogenated hydrocarbons such as dichloromethane, dichloroethane and mixtures of the abovementioned solvents. To prepare the aqueous composition according to the invention, the resulting solid solution of
Wirkstoffs in der amphiphilen Polymerzusammensetzung in einem wässrigen Medium durch Rühren dispergieren. Das Rühren kann bei Temperaturen im Bereich der Umgebungstemperatur als auch bei erhöhter Temperatur erfolgen, beispielsweise bei einer Temperatur im Bereich von 10 bis 80 °C und insbesondere im Bereich von 20 bis 50 °C.Disperse agent in the amphiphilic polymer composition in an aqueous medium by stirring. The stirring can be carried out at temperatures in the range of the ambient temperature as well as at elevated temperature, for example at a temperature in the range of 10 to 80 ° C and in particular in the range of 20 to 50 ° C.
In einer zweiten Ausführungsform der vorliegenden Erfindung erfolgt die Herstellung der wässrigen Wirkstoffzusammensetzung durch Einarbeiten des Wirkstoffs und/oder Effektstoffs in eine wässrige Lösung/Dispersion der amphiphilen Polymerzusammensetzung. Hierzu geht man in der Regel so vor, das man das Einarbeiten bei einer Tem- peratur durchführt, die oberhalb der Schmelztemperatur des Wirk- bzw. Effektstoffs liegt und vorzugsweise bei einer Temperatur, bei der die Wirk- bzw. Effektstoffschmelze niedrigviskos ist, d. h. eine Viskosität im Bereich von 1 bis 1000 mPa.s (nach DIN 53019-2 bei 25°C) aufweist. Vorzugsweise erfolgt das Einarbeiten unter Anwendung von starken Scherkräften, beispielsweise in einem Ultraturrax. In einer dritten Ausführungsform der Erfindung erfolgt die Herstellung der wässrigen Wirkstoffzusammensetzung durch ein Verfahren umfassend die folgenden Schritte a bis c:In a second embodiment of the present invention, the preparation of the aqueous active ingredient composition is carried out by incorporation of the active ingredient and / or effect substance in an aqueous solution / dispersion of the amphiphilic polymer composition. For this purpose, the procedure is usually such that the incorporation is carried out at a temperature which is above the melting point of the active substance or effect substance and preferably at a temperature at which the active substance or effect substance melt is of low viscosity, ie one Viscosity in the range of 1 to 1000 mPa.s (according to DIN 53019-2 at 25 ° C). Preferably, the incorporation is carried out using strong shear forces, for example in an Ultraturrax. In a third embodiment of the invention, the preparation of the aqueous active substance composition is carried out by a process comprising the following steps a to c:
a) Herstellung einer Lösung von Wirkstoff und/oder Effektstoff und gegebenenfalls amphiphiler Polymerzusammensetzung in einem organischen Lösungsmittel, das einen Siedepunkt unter dem von Wasser aufweist und b) Vermischen der Lösung des Wirkstoffs und/oder Effektstoffs mit Wasser oder mit einer wässrigen Lösung des amphiphilen Copolymeren und c) Entfernen des Lösungsmittels.a) preparation of a solution of active ingredient and / or effect substance and optionally amphiphilic polymer composition in an organic solvent which has a boiling point below that of water and b) mixing the solution of the active ingredient and / or effect substance with water or with an aqueous solution of the amphiphilic copolymer and c) removing the solvent.
Hierbei kann man alternativ so vorgehen, dass die Lösung des Wirkstoffs die amphiphile Polymerzusammensetzung enthält und man diese Lösung mit Wasser vermischt oder dass die Lösung des Wirkstoffs nur einen Teil der amphiphilen Polymerzusam- mensetzung oder keine amphiphile Polymerzusammensetzung enthält und man diese Lösung mit einer wässrigen Lösung oder Dispersion der amphiphilen Polymerzusammensetzung vermischt. Das Vermischen kann in geeigneten Rührgefäßen erfolgen, wobei man sowohl Wasser oder die wässrige Lösung der amphiphilen Polymerzusammensetzung vorlegen kann und hierzu die Lösung des Wirk- oder Effektstoffs gibt, oder alternativ die Lösung des Wirk- oder Effektstoffs vorlegt und hierzu das Wasser bzw. die wässrige Lösung der amphiphilen Polymerzusammensetzung gibt. Anschließend entfernt man das organische Lösungsmittel, z.B. durch Destillation, wobei man gegebenenfalls Wasser zusetzt.Here, one can alternatively proceed so that the solution of the active substance contains the amphiphilic polymer composition and this solution is mixed with water or that the solution of the active ingredient contains only part of the amphiphilic polymer composition or no amphiphilic polymer composition and this solution is mixed with an aqueous solution or dispersion of the amphiphilic polymer composition. The mixing can be carried out in suitable stirred vessels, wherein it is possible to submit both water or the aqueous solution of the amphiphilic polymer composition and for this purpose gives the solution of the active or effect substance, or alternatively presents the solution of the active or effect substance and for this purpose the water or the aqueous Solution of amphiphilic polymer composition gives. Subsequently, the organic solvent, e.g. by distillation, optionally adding water.
In einer bevorzugten Variante dieser Ausführungsform gibt man die Wirkstofflösung und das Wasser bzw. die wässrige Lösung der amphiphilen Polymerzusammen- . setzung kontinuierlich in eine Mischzone und entnimmt dieser kontinuierlich die Mischung, aus der man anschließend das Lösungsmittel entfernt. Die Mischzone kann beliebig ausgestaltet werden. Grundsätzlich sind hierfür alle Apparaturen geeignet, die ein kontinuierliches Mischen von Flüssigkeitsströmen ermöglichen. Derartige Apparaturen sind bekannt, z. B. aus Continuous Mixing of Fluids (J.-H. Henzler) in Ullmann's Encyclopedia 5th ed. on CD-Rom, Wiley-VCH. Die Mischzone können als statische oder dynamische Mischer oder Mischformen davon ausgestaltet sein. Als Mischzonen kommen insbesondere auch Jet-Mischer oder vergleichbare Mischer mit Düsen in Be- tracht. In einer bevorzugten Ausgestaltung handelt es sich bei der Mischzone um die im „Handbook of Industrial Crystallization" (A.S.Myerson, 1993 Butterworth- Heinemann, Seite 139, ISBN 0-7506-9155-7) beschriebene Apparatur oder eine vergleichbare Apparatur. Das Volumenverhältnis von Wirkstofflösung zu Wasser bzw. wässriger Lösung der amphiphilen Polymerzusammensetzung kann über weite Bereich variiert werden und liegt vorzugsweise im Bereich von 10:1 bis 1 :20 und insbesondere im Bereich von 5:1 bis 1 :10.In a preferred variant of this embodiment, the active substance solution and the water or the aqueous solution of the amphiphilic polymer combination are added. continuously in a mixing zone and this takes continuously from the mixture, from which one then removes the solvent. The mixing zone can be configured as desired. Basically, all apparatuses are suitable for this, which allow a continuous mixing of liquid streams. Such apparatuses are known, for. From Continuous Mixing of Fluids (J.H.Henzler) in Ullmann's Encyclopedia 5th ed. On CD-Rom, Wiley-VCH. The mixing zone may be configured as static or dynamic mixers or mixed forms thereof. In particular, jet mixers or comparable mixers with nozzles are also considered as mixing zones. In a preferred embodiment, the mixing zone is the apparatus described in the Handbook of Industrial Crystallization (ASMyerson, 1993 Butterworth-Heinemann, page 139, ISBN 0-7506-9155-7) or a comparable apparatus. The volume ratio of drug solution to water or aqueous solution of the amphiphilic polymer composition can be varied over a wide range and is preferably in the range from 10: 1 to 1:20 and in particular in the range from 5: 1 to 1:10.
Naturgemäß sollte das Lösungsmittel geeignet sein, die amphiphile Polymerzusammensetzung und den Wirkstoff in den gewünschten Mengenverhältnissen zu lösen. Geeignete Lösungsmittel kann der Fachmann durch Routineexperimente ermitteln. Beispiele für geeignete Lösungsmittel sind C2-C -Alkanole wie Ethanol, n-Propanol, n-Butanol, Isobutanol, die vorgenannten aliphatischen und alicyclischen Ether wie Diethylether, Diisopropylether, Methyl-tert.-butylether, Dioxan, Tetrahydrofu- ran, Ketone wie Aceton, Methylethylketon.Naturally, the solvent should be able to dissolve the amphiphilic polymer composition and the active ingredient in the desired proportions. Suitable solvents can be determined by those skilled in the art by routine experimentation. Examples of suitable solvents are C 2 -C 4 -alkanols, such as ethanol, n-propanol, n-butanol, isobutanol, the abovementioned aliphatic and alicyclic ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran, ketones, such as Acetone, methyl ethyl ketone.
In einer weiteren Ausführungsform der vorliegenden Erfindung stellt man eine nicht- wässrige Wirkstoffzusammensetzung her, indem man eine homogene, nicht wässrige Mischung aus amphiphiler Polymerzusammensetzung und Wirkstoff und/oder Effektstoff herstellt. Diese Zusammensetzung ist, wenn Sie keine flüssigen Bestandteile enthält, in der Regel fest. Bezüglich der Herstellung solcher Zusammensetzungen gilt das zuvor im Zusammenhang mit der ersten Ausführungsform für die Herstellung einer homogenen, nicht wässrige Mischung, bestehend aus amphiphiler Polymerzusammensetzung und Wirkstoff und/oder Effektstoff, gesagte in analoger Weise, jedoch können an dieser Stelle gegebenenfalls gewünschte Additive und Hilfsmittel in an sich bekannter Weise in die Zusammensetzung eingearbeitet werden. Diese Variante eignet sich insbesondere zur Herstellung nicht-wässriger Zusammensetzungen.In a further embodiment of the present invention, a non-aqueous active ingredient composition is prepared by preparing a homogeneous, non-aqueous mixture of amphiphilic polymer composition and active ingredient and / or effect substance. This composition is usually solid if it contains no liquid ingredients. With regard to the preparation of such compositions, what has been said previously in connection with the first embodiment for the preparation of a homogeneous, non-aqueous mixture consisting of amphiphilic polymer composition and active ingredient and / or effect substance in an analogous manner, but optionally at this point desired additives and auxiliaries be incorporated into the composition in a conventional manner. This variant is particularly suitable for the preparation of non-aqueous compositions.
In den erfindungsgemäßen Wirkstoffzusammensetzungen hat es sich als vorteilhaft erwiesen, wenn das Gewichtsverhältnis von Wirkstoff und/oder Effektstoff zur amphiphilen Polymerzusammensetzung im Bereich von 1 :10 bis 3:1 und insbesondere im Bereich von 1 :5 bis 2:1 liegt.In the active substance compositions according to the invention, it has proved to be advantageous if the weight ratio of active ingredient and / or effect substance to the amphiphilic polymer composition is in the range from 1:10 to 3: 1 and in particular in the range from 1: 5 to 2: 1.
Der Gehalt an Wirk- und/oder Effektstoff kann über weite Bereiche variiert werden. Insbesondere ermöglichen die amphiphilen Polymerzusammensetzungen das Herstellen von so genannten Wirkstoffkonzentraten, welche den Wirkstoff in einer Menge von wenigstens 5 Gew.-%, z. B. in einer Menge von 5 bis 50 Gew.-% und insbesondere in einer Menge von 5 bis 20 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung, enthalten.The content of active and / or effect substance can be varied over wide ranges. In particular, the amphiphilic polymer compositions permit the preparation of so-called active agent concentrates containing the active ingredient in an amount of at least 5% by weight, e.g. B. in an amount of 5 to 50 wt .-% and in particular in an amount of 5 to 20 wt .-%, based on the total weight of the composition.
Vorteilhafterweise können die erfindungsgemäßen Zusammensetzungen, insbesondere die wässrigen Wirkstoffzusammensetzungen, lösungsmittelfrei oder lösungsmittel- arm formuliert werden, d. h. der Anteil an flüchtigen Bestandteilen in derAdvantageously, the compositions according to the invention, in particular the aqueous active compound compositions, can be formulated solvent-free or low-solvent, ie. H. the percentage of volatile components in the
Wirkstoffzusammensetzung beträgt häufig nicht mehr als 10 Gew.-%, insbesondere Wirkstoffzusammensetzung beträgt häufig nicht mehr als 10 Gew.-%, insbesondere nicht mehr als 5 Gew.-% und speziell nicht mehr als 1 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung. Flüchtige Bestandteile sind dabei solche, die bei Normaldruck einen Siedepunkt unterhalb 200 °C aufweisen.Active ingredient composition is often not more than 10 wt .-%, in particular Active ingredient composition is often not more than 10% by weight, in particular not more than 5% by weight and especially not more than 1% by weight, based on the total weight of the composition. Volatile constituents are those which have a boiling point below 200 ° C. under atmospheric pressure.
In den erfindungsgemäßen Zusammensetzungen können eine Vielzahl unterschiedlicher Wirk- und Effektstoffe formuliert werden. Eine besondere Ausführungsform der Erfindung betrifft die Formulierung von Wirkstoffen für den Pflanzenschutz, d. h. von Herbiziden, Fungiziden, Nematiziden, Akariziden, Insektiziden sowie Wirkstoffen, die das Pflanzenwachstum regulieren.In the compositions of the invention, a variety of different active and effect substances can be formulated. A particular embodiment of the invention relates to the formulation of active ingredients for crop protection, d. H. of herbicides, fungicides, nematicides, acaricides, insecticides and plant growth regulators.
Beispiele für fungizide Wirkstoffe, die als erfindungsgemäße Wirkstoffzusammensetzung formuliert werden können, umfassen: • Acylalanine wie Benalaxyl, Metalaxyl, Ofurace, Oxadixyl; • Aminderivate wie Aldimorph, Dodine, Dodemorph, Fenpropimorph, Fenpropidin, Guazatine, Iminoctadine, Spiroxamin, Tridemorph; • Anilinopyrimidine wie Pyrimethanil, Mepanipyrim oder Cyrodinyl; • Antibiotika wie Cycloheximid, Griseofulvin, Kasugamycin, Natamycin, Polyoxin, Streptomycin und Validamycin A; • Azole wie Bitertanol, Bromuconazole, Cyazofamid, Cyproconazole, Difenoco- nazole, Dinitroconazole, Epoxiconazol, Etridazole, Fenbuconazole, Fluquinco- nazole, Flusilazole, Flutriafol, Fuberidazol, Hexaconazol, Hymexazol, Imazalil, Ipconazole, Imibenconazol, Metconazole, Myclobutanil, Penconazole, Perfua- zorate, Propiconazole, Prochloraz, Prothioconazole, Simeconazole, Tebucona- zole, Tetraconazole, Thiabendazol, Triadimefon, Triadimenol, Triflumizol, Triti- conazol, 2-Butoxy-6-iod-3-propylchromen-4-on, 3-(3-Brom-6-fluor-2-methylindol-1 - sulfonyl)-[1 ,2,4]triazol-1 -sulfonsäuredimethylamid; • 2-Methoxybenzophenone, wie sie in EP-A 897904 durch die allgemeine Formel I beschrieben werden, z. B. Metrafenon; • Dicarboximide wie Iprodion, Myclozolin, Procymidone, Vinclozolin; • Dithiocarbamate wie Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamat, Thiram, Ziram, Zineb; • Heterocyclische Verbindungen wie Anilazine, Benomyl, Boscalid, Carbendazim, Carboxin, Oxycarboxin, Cyazofamid, Dazomet, Dithianon, Ethirimol, Dimethirimol, Famoxadon, Fenamidon, Fenarimol, Fuberidazole, Flutolanil, Furametpyr, Isoprothiolane, Mepronil, Nuarimol, Octhilinone, Picobezamid, Probenazole, Proquinazid, Pyrifenox, Pyroquilon, Quinoxyfen, Silthiofam; Thiabendazole, Thifluzamid, Thiophanat-methyl, Tiadinil, Tricyclazole, Triforine, 3-[5-(4-Chlorphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, und Bupirimate;Examples of fungicidal active compounds that can be formulated as active ingredient composition according to the invention include: acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl; Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph; Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl; Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxine, streptomycin and validamycin A; • Azoles such as bitertanol, bromuconazole, cyazofamide, cyproconazole, difenocynazole, dinitroconazole, epoxiconazole, etridazole, fenbuconazole, fluquinocynazole, flusilazole, flutriafol, fuberidazole, hexaconazole, hymexazole, imazalil, ipconazole, imibenconazole, metconazole, myclobutanil, penconazole, perfume - zorates, propiconazole, prochloraz, prothioconazole, simeconazole, tebuconazole, tetraconazole, thiabendazole, triadimefon, triadimol, triflumizole, triticonazole, 2-butoxy-6-iodo-3-propylchromen-4-one, 3- (3 Bromo-6-fluoro-2-methylindole-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide; 2-Methoxybenzophenones, as described in EP-A 897,904 by the general formula I, z. Eg metrafenone; Dicarboximides such as iprodione, myclozoline, procymidones, vinclozolin; Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamate, Thiram, Ziram, Zineb; Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxine, cyazofamide, dazomet, dithianone, ethirimol, dimethirimol, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolanes, mepronil, nuarimol, octhilinone, picobezamide, probenazoles, Proquinazide, Pyrifenox, Pyroquilon, Quinoxyfen, Silthiofam; Thiabendazoles, thifluzamide, thiophanate-methyl, tiadinil, tricyclazoles, triforines, 3- [5- (4-chlorophenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridines, and bupirimate;
• Nitrophenylderivative wie Binapacryl, Dinocap, Dinobuton, Nitrophthal- isopropyl; • Phenylpyrrole wie Fenpiclonil sowie Fludioxonil;Nitrophenyl derivatives such as binapacryl, dinocap, dinobutone, nitrophthalic isopropyl; Phenylpyrroles such as fenpiclonil and fludioxonil;
• nicht klassifizierte Fungizide wie Acibenzolar-S-methyl, Benthiavalicarb, Carpropamid, Chlorothalonil, Cyflufenamid, Cymoxanil, Diciomezin, Diciocymet, Diethofencarb, Edifenphos, Ethaboxam, Fenhexamid, Fentin-Acetat, Fenoxanil, Ferimzone, Fluazinam, Fosetyl, Fosetyl-Aluminum, Iprovalicarb, Hexachlorobenzol, Metrafenon, Pencycuron, Propamocarb, Phthalide, Toloclofos-Methyl, Quintozene, Zoxamid, Isoprothiolan, Fluopicolide (Picobenzamid); Carpropamid, Mandipropamid, N-(2-{4-[3-(4-Chlorphenyl)-prop-2- inyloxy]-3-methoxyphenyl}ethyl)-2-methansulfonylamino-3-methyl-butyramid, N-(2-{4-[3-(4-Chlorphenyl)-prop-2-inyloxy]-3-methoxyphenyl}-ethyl)-2-ethansulfonyl- amino-3-methylbutyramid; Furametpyr, Thifluzamide, Penthiopyrad, Fenhexamid, 3,4-Dichlorisothiazol-5-carboonsäure-(2-cyano-phenyl)-amide, Flubenthiavalicarb, 3-(4-Chlorphenyl)-3-(2-isopropoxycarbonylamino-3-methyl-butyrylamino)- propionsäuremethylester, {2-Chlor-5-[1-(6-methylpyridin-2-ylmethoxyimino)-ethyl]- benzyl}-carbaminsäuremethylester, {2-Chlor-5-[1-(3-methylbenzyloxyimino)-ethyl]- benzylj-carbaminsäuremethylester, Flusulfamide, Amide der FormelUnclassified fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, diciomezine, diciocymet, diethofencarb, edifenphos, ethaboxam, fenhexamide, fentin-acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb , Hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalides, toloclofos-methyl, quintozene, zoxamide, isoprothiolane, fluopicolide (picobenzamide); Carpropamide, mandipropamide, N- (2- {4- [3- (4-chlorophenyl) -prop-2-ynyloxy] -3-methoxyphenyl} ethyl) -2-methanesulfonylamino-3-methylbutyramide, N- (2- {4- [3- (4-chlorophenyl) -prop-2-ynyloxy] -3-methoxyphenyl} -ethyl) -2-ethanesulfonylamino-3-methylbutyramide; Furametpyr, thiflucamide, penthiopyrad, fenhexamid, 3,4-dichloroisothiazole-5-carboonic acid (2-cyano-phenyl) -amide, flubenthiavalicarb, 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methyl-butyrylamino methyl propionate, {2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl} -carbamic acid methyl ester, {2-chloro-5- [1- (3-methylbenzyloxyimino) -ethyl] - Benzylj-carbamic acid methyl ester, Flusulfamide, amides of the formula
Figure imgf000026_0001
worin X für CHF oder CH3; und R1,R2 unabhängig voneinander für Halogen, Methyl oder Halogenmethyl, z. B. CF3; stehen;
Figure imgf000026_0001
wherein X is CHF or CH 3 ; and R 1 , R 2 are independently halogen, methyl or halomethyl, e.g. CF 3 ; stand;
• Strobilurine wie sie in WO 03/075663 durch die allgemeine Formel I beschrieben werden, beispielsweise Azoxystrobin, Dimoxystrobin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin sowie Trifloxystrobin;Strobilurins as described in WO 03/075663 by the general formula I, for example azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin;
• Sulfensäure-Derivative wie Captafol, Captan, Dichlofluanid, Folpet, Tolylfluanid;Sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid;
• Zimtsäureamide und Analoga wie Dimethomorph, Flumetover, Flumorp;Cinnamic acid amides and analogs such as dimethomorph, flumetover, flumorp;
• 6-Aryl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine wie sie z. B. in WO 98/46608, WO 99,41255 oder WO 03/004465 jeweils durch die allgemeine Formel I be- schrieben werden, z. B. 5-Chlor-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorphenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidin; • Amidfungizide wie Cyclofenamid sowie (Z)-N-[α-(Cyclopropylmethoxyimino)- 2,3-difluoro-6-(difluoromethoxy)benzyl]-2-phenylacetamid.6-aryl- [1,2,4] triazolo [1,5-a] pyrimidines as described, for example, in US Pat. In WO 98/46608, WO 99/41255 or WO 03/004465 in each case by the general formula I be written, z. For example, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine; Amide fungicides such as cyclofenamide and (Z) -N- [α- (cyclopropylmethoxyimino) -2,3-difluoro-6- (difluoromethoxy) benzyl] -2-phenylacetamide.
Beispiele für Herbizide, die als erfindungsgemäße wässrige Wirkstoffzusammensetzung formuliert werden können, umfassen:Examples of herbicides that can be formulated as the aqueous active ingredient composition of the present invention include:
1 ,3,4-Thiadiazole wie Buthidazole und Cyprazole; Amide wie Allidochlor, Benzoylpropethyl, Bromobutide, Chlorthiamid, Dimepipe- rate, Dimethenamid, Diphenamid, Etobenzanid, Flampropmethyl, Fosamin, Iso- xaben, Metazachlor, Monalide, Naptalam, Pronamid, Propanil; Aminophosphorsäuren wie Bilanafos, Buminafos, Glufosinateammonium, Glyphosate, Sulfosate; Aminotriazole wie Amitrol, Anilide wie Anilofos, Mefenacet; Aryloxyalkan-säure wie 2,4-D, 2,4-DB, Clomeprop, Dichlorprop, Dichlorprop-P, Fenoprop, Fluroxypyr, MCPA, MCPB, Mecoprop, Mecoprop-P, Napropamide, Napropanilide, Triclopyr; Benzoesäuren wie Chloramben, Dicamba; Benzothiadiazinone wie Bentazon; Bleacher wie Clomazone, Diflufenican, Fluorochloridone, Flupoxam, Fluridone, Pyrazolate, Sulcotrione; Carbamate wie Carbetamid, Chlorbufam, Chlorpropham, Desmedipham, Phenmedipham, Vernolate; Chinolinsäuren wie Quinclorac, Quinmerac; Dichlorpropionsäuren wie Dalapon; Dihydrobenzofurane wie Ethofumesate; Dihydrofuran-3-on wie Flurtamone; Dinitroaniline wie Benefin, Butralin, Dinitramin, Ethalfluralin, Fluchloralin, Iso- propalin, Nitralin, Oryzalin, Pendimethalin, Prodiamine, Profluralin, Trifluralin, Dinitrophenole wie Bromofenoxim, Dinoseb, Dinoseb-acetat, Dinoterb, DNOC, Minoterb-Acetat; Diphenylether wie Acifluorfen-sodium, Aclonifen, Bifenox, Chlornitrofen, Difenoxuron, Ethoxyfen, Fluorodifen, Fluoroglycofen-ethyl, Fomesafen, Fury- loxyfen, Lactofen, Nitrofen, Nitrofluorfen, Oxyfluorfen; Dipyridyle wie Cyperquat, Difenzoquat-methylsulfat, Diquat, Paraquat-dichlorid; Imidazole wie Isocarbamid; • Imidazolinone wie Imazamethapyr, Imazapyr, Imazaquin, Imazethabenz-methyl, Imazethapyr, Imazapic, Imazamox;1, 3,4-thiadiazoles such as buthidazole and cyprazole; Amides such as allidochlor, benzoylpropyl, bromobutide, chlorthiamide, dimepiperate, dimethenamid, diphenamid, etobenzanide, flampropmethyl, fosamine, isoxaben, metazachlor, monalides, naptalam, pronamide, propanil; Aminophosphoric acids such as bilanafos, buminafos, glufosinate-ammonium, glyphosate, sulfosates; Aminotriazoles such as amitrole, anilides such as anilofos, mefenacet; Aryloxyalkanoic acid such as 2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P, fenoprop, fluroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide, napropanilides, triclopyr; Benzoic acids such as Chloramben, Dicamba; Benzothiadiazinones such as bentazone; Bleachers such as Clomazone, Diflufenican, Fluorochloridone, Flupoxam, Fluridone, Pyrazolate, Sulcotrione; Carbamates such as carbetamide, chlorobufam, chlorpropham, desmedipham, phenmedipham, vernolates; Quinolinic acids such as Quinclorac, Quinmerac; Dichloropropionic acids such as Dalapon; Dihydrobenzofurans such as ethofumesates; Dihydrofuran-3-one such as flurtamone; Dinitroanilines such as benefin, butraline, dinitramine, ethalfluralin, fluchloralin, isopropaline, nitralin, oryzalin, pendimethalin, prodiamine, profluralin, trifluralin, dinitrophenols such as bromofenoxime, dinoseb, dinoseb acetate, dinoterb, DNOC, minoterb acetate; Diphenyl ethers such as acifluorfen-sodium, aclonifen, bifenox, chloronitrofen, difenoxuron, ethoxyfen, fluorodifene, fluoroglycofenethyl, fomesafen, ful- lylfenfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen; Dipyridyls such as cyperquat, difenzoquat-methylsulfate, diquat, paraquat-dichloride; Imidazoles such as isocarbamide; Imidazolinones such as imazamethapyr, imazapyr, imazaquin, imazethabenz-methyl, imazethapyr, imazapic, imazamox;
• Oxadiazole wie Methazole, Oxadiargyl, Oxadiazon;Oxadiazoles such as methazoles, oxadiargyl, oxadiazon;
• Oxirane wie Tridiphane; • Phenole wie Bromoxynil, loxynil;• oxiranes like Tridiphane; Phenols, such as bromoxynil, loxynil;
• Phenoxyphenoxypropionsäureester wie Clodinafop, Cyhalofop-butyl, Diclofop- methyl, Fenoxaprop-ethyl, Fenoxaprop-p-ethyl, Fenthiapropethyl, Fluazifop- butyl, Fluazifop-p-butyl, Haloxyfop-ethoxy-ethyl, Haloxyfop-methyl, Haloxyfop-p- methyl, Isoxapyrifop, Propaquizafop, Quizalofop-ethyl, Quizalofop-p-ethyl, Qui- zalofop-tefuryl; Phenylessigsäuren wie Chlorfenac; Phenylpropionsäuren wie Chlorophenprop-methyl; ppi-Wirkstoffe wie Benzofenap, Flumiclorac-pentyl, Flumioxazin, Flumipropyn, Flupropacil, Pyrazoxyfen, Sulfentrazone, Thidiazimin; • Pyrazole wie Nipyraclofen; Pyridazine wie Chloridazon, Maleic hydrazide, Norflurazon, Pyridate; Pyridincarbonsäuren wie Clopyralid, Dithiopyr, Picloram, Thiazopyr; Pyrimidylether wie Pyrithiobacsäure, Pyrithiobac-sodium, KIH-2023, KIH-6127; Sulfonamide wie Flumetsulam, Metosulam; • Triazolcarboxamide wie Triazofenamid; Uracile wie Bromacil, Lenacil, Terbacil; ferner Benazolin, Benfuresate, Bensulide, Benzofluor, Bentazon, Butamifos, Cafenstrole, Chlorthal-dimethyl, Cinmethylin, Dichlobenil, Endothall, Fluorben- tranil, Mefluidide, Perfluidone, Piperophos, Topramezone und Prohexadion- Calcium;Phenoxyphenoxypropionic acid esters such as clodinafop, cyhalofop-butyl, diclofopmethyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, fenthiapropethyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-p-methyl , Isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-p-ethyl, quizalofop-tefuryl; Phenylacetic acids such as chlorfenac; Phenylpropionic acids such as chlorophenprop-methyl; ppi agents such as benzofenap, flumiclorac-pentyl, flumioxazine, flumipropyne, flupropacil, pyrazoxyfen, sulfentrazone, thidiazimin; • pyrazoles such as Nipyraclofen; Pyridazines such as Chloridazon, Maleic hydrazide, Norflurazon, Pyridate; Pyridinecarboxylic acids such as clopyralid, dithiopyr, picloram, thiazopyr; Pyrimidyl ethers such as pyrithiobacic acid, pyrithiobac-sodium, KIH-2023, KIH-6127; Sulfonamides such as flumetsulam, metosulam; Triazole carboxamides such as triazofenamide; Uracils such as bromacil, lenacil, terbacil; Benazoline, Benfuresate, Bensulide, Benzofluor, Bentazone, Butamifos, Cafenstrole, Chlorthal-dimethyl, Cinmethylin, Dichlobenil, Endothall, Fluoroben- tranil, Mefluidide, Perfluidone, Piperophos, Topramezone and Prohexadione-Calcium;
• Sulfonylharnstoffe wie Amidosulfuron, Azimsulfuron, Bensulfuron-methyl, Chlorimuron-ethyl, Chlorsulfuron, Cinosulfuron, Cyclosulfamuron, Ethametsulfu- ron-methyl, Flazasulfuron, Halosulfuron-methyl, Imazosulfuron, Metsulfuron- methyl, Nicosulfuron, Primisulfuron, Prosulfuron, Pyrazosulfuron-ethyl, Rimsul- furon, Sulfometuron-methyl, Thifensulfuron-methyl, Triasulfuron, Tribenuron- methyl, Triflusulfuron-methyl, Tritosulfuron;Sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron-ethyl, Rimsul - furon, sulfometuron-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, tritosulfuron;
• Pflanzenschutz-Wirkstoffe vom Cyclohexenon-Typ wie Alloxydim, Clethodim, Cloproxydim, Cycloxydim, Sethoxydim und Tralkoxydim. Ganz besonders bevorzugte herbizide Wirkstoffe vom Cyclohexenon-Typ sind: Tepraloxydim (vgl. AGROW, Nr. 243, 3.11.95, Seite 21 , Caloxydim) und 2-(1 -[2-{4- Chlorphenoxy}propyl-oxyimino]butyl)-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)- 2-cyclohexen-1 -on und vom Sulfonylharnstoff-Typ: N-(((4-methoxy-6- [trifluormethyl]-1 ,3,5-triazin-2-yl)amino)carbo-nyl)-2-(trifluormethyl)- benzolsulfonamid.• Cyclohexenone-type pesticides such as alloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim and tralkoxydim. Very particularly preferred cyclohexenone-type herbicidal active compounds are: tepraloxydim (compare AGROW, No. 243, 3.11.95, page 21, caloxydim) and 2- (1 - [2- {4-chlorophenoxy} propyl-oxyimino] butyl) 3-hydroxy-5- (2H-tetrahydrothiopyran-3-yl) -2-cyclohexene-1 -one and of the sulfonylurea type: N - (((4-methoxy-6- [trifluoromethyl] -1,3,5 triazin-2-yl) amino) carbo-nyl) -2- (trifluoromethyl) - benzenesulfonamide.
Beispiele für Insektizide, die als erfindungsgemäße wässrige Wirkstoffzusammensetzung formuliert werden können, umfassen:Examples of insecticides that can be formulated as the aqueous active agent composition of the present invention include:
• Organo(thio)phosphate wie Acephate, Azamethiphos, Azinphos-methyl, Chlor- pyrifos, Chlorpyrifos-methyl, Chlorfenvinphos, Diazinon, Dichlorphos, Dimethyl- vinphos, Dioxabenzofos, Dicrotophos, Dimethoate, Disulfoton, Ethion, EPN, Fenitrothion, Fenthion, Isoxathion, Malathion, Methamidophos, Methidathion, Methyl-Parathion, Mevinphos, Monocrotophos, Oxydemeton-methyl, Paraoxon, Parathion, Phenthoate, Phosalone, Phosmet, Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Primiphos-ethyl, Pyraclofos, Pyri- daphenthion, Sulprophos, Triazophos, Trichlorfon; Tetrachlorvinphos, Vami- dothionOrgano (thio) phosphates, such as acephates, azamethiphos, azinphos-methyl, chloropyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorophos, dimethylvinphos, dioxabenzofos, dicrotophos, dimethoates, disulphoton, ethion, EPN, fenitrothion, fenthion, isoxathion , Malathion, Methamidophos, Methidathione, Methyl Parathion, Mevinphos, Monocrotophos, Oxydemeton-methyl, Paraoxone, Parathion, Phenthoate, Phosalone, Phosmet, Phosphamidone, Phorates, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Primiphos-ethyl, Pyraclofos, Pyri - dapendhion, sulprophos, triazophos, trichlorfon; Tetrachlorvinphos, vami- dothione
• Carbamate wie Alanycarb, Benfuracarb, Bendiocarb, Carbaryl, Carbofuran, Carbosulfan, Fenoxycarb, Furathiocarb, Indoxacarb, Methiocarb, Methomyl, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Triazamate; • Pyrethroide wie Allethrin, Bifenthrin, Cyfluthrin.Cyphenothrin, Cycloprothrin, Cy- permethrin, Deltamethrin, Esfenvalerate, Ethofenprox, Fenpropathrin, Fenvale- rate, Cyhalothrin, Lambda-Cyhalothrin, Imoprothrin, Permethrin, Prallethrin, Py- rethrin I, Pyrethrin II, Silafluofen, Tau-Fluvalinate, Tefluthrin, Tralomethrin, Transfluthrin, alpha-Cypermethrin, Zeta-Cypermethrin, Permethrin;Carbamates such as alanycarb, benfuracarb, bendiocarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, indoxacarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamates; Pyrethroids such as allethrin, bifenthrin, cyfluthrin, cyphenothrin, cycloprothrin, cyperethrin, deltamethrin, esfenvalerate, ethofenprox, fenpropathrin, fenvalate, cyhalothrin, lambda-cyhalothrin, imoprothrin, permethrin, prallethrin, pyherhrin I, pyrethrin II, silafluofen , Tau-fluvalinate, tefluthrin, tralomethrin, transfluthrin, alpha-cypermethrin, zeta-cypermethrin, permethrin;
• Arthropode Wachstumsregulatoren: a) Chitinsyntheseinhibitoren z. B. Benzoyl- hamstoffe wie Chlorfluazuron, Cyromacin, Diflubenzuron, Flucycloxuron, Flufe- noxuron, Hexaflumuron, Lufenuron, Novaluron, Teflubenzuron, Triflumuron; Buprofezin, Diofenolan, Hexythiazox, Etoxazole, Clofentazine; b) Ecdysone An- tagonisten wie Halofenozide, Methoxyfenozide, Tebufenozide; c) Juvenoide wie Pyriproxyfen, Methoprene, Fenoxycarb; d) Lipid-Biosyntheseinhibitoren wie Spi- rodiclofen;• Arthropod growth regulators: a) chitin synthesis inhibitors z. B. benzoylureas such as chlorofluorazuron, cyromacin, diflubenzuron, flucycloxuron, flufenonoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; Buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists such as halofenozides, methoxyfenozides, tebufenozides; c) juvenoids such as pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors such as spiroidalofen;
• Neonicotinoide wie Flonicamid, Clothianidin, Dinotefuran, Imidacloprid, Thia- methoxam, Nitenpyram, Nithiazin, Acetamiprid, Thiacloprid;Neonicotinoids such as flonicamid, clothianidin, dinotefuran, imidacloprid, thiomethoxam, nitenpyram, nithiazine, acetamiprid, thiacloprid;
Weitere unklassifizierte Insektizide wie Abamectin, Acequinocyl, acetamiprid, A- mitraz, Azadirachtin, Bensultap, Bifenazate, Cartap, Chlorfenapyr, Chlordime- form, Cyromazine, Diafenthiuron, Dinetofuran, Diofenolan, Emamectin, Endo- sulfan, Ethiprole, Fenazaquin, Fipronil, Formetanate, Formetanate hydrochlorid, gamma-HCH Hydramethylnon, Imidacloprid, Indoxacarb, Isoprocarb, Metolcarb, Pyridaben, Pymetrozine, Spinosad, Tebufenpyrad, Thiamethoxam, Thiocyclam, Pyridalyl, Flonicamid, Fluacypyrim, Milbemectin, Spiromesifen, Flupyrazofos, NC 512, Tolfenpyrad, Flubendiamide, Bistrifluron, Benclothiaz, Pyrafluprole, Py- riprole, Amidoflumet, Flufenerim, Cyflumetofen, Acequinocyl, Lepimectin, Profluthrin, Dimefluthrin, Amidrazone, Metaflumizone, N-R'-2,2-Dihalo-1 -R"- cyclopropancarboxamid-2-(2,6-dichlor-α,α,α-tri-fluor-p-tolyl)hydrazon, N-R'-2,2- di(R'")propionamid-2-(2,6-dichlor-α,α,α-trifluor-p-tolyl)-hydrazon1 wobei halo für Chlor oder Brom, R' für Methyl oder Ethyl, R" für Wasserstoff oder Methyl und R'" für Methyl oder Ethyl stehen, XMC und Xylylcarb sowie Verbindungen der folgenden FormelOther unclassified insecticides such as abamectin, acequinocyl, acetamiprid, a-mitraz, azadirachtin, bensultap, bifenazate, cartap, chlorfenapyr, chlordime form, cyromazine, diafenthiuron, dinetofuran, diofenolan, emamectin, endo- sulfan, ethiprole, fenazaquin, fipronil, formetanate, formetanate hydrochloride, gamma-HCH hydramethylnone, imidacloprid, indoxacarb, isoprocarb, metolcarb, pyridaben, pymetrozine, spinosad, tebufenpyrad, thiamethoxam, thiocyclam, pyridalyl, flonicamid, fluacypyrim, milbemectin, spiromesifen, flupyrazofos, NC 512, tolfenpyrad, flubendiamide, bis-trifluron, benclothiaz, pyrafluprole, pyriprole, amidoflumet, flufenerim, cyflumetofen, acequinocyl, lepimectin, profluthrin, dimefluthrin, amidrazone, metaflumizone, N-R'-2,2-dihalo-1-R " - cyclopropanecarboxamide-2- (2,6-dichloro-α, α, α-trifluoro-p-tolyl) hydrazone, N-R'-2,2-di (R '") propionamide-2- (2, 6-dichloro-α, α, α-trifluoro-p-tolyl) hydrazone 1 where halo is chlorine or bromine, R 'is methyl or ethyl, R "is hydrogen or methyl and R'" is methyl or ethyl, XMC and xylylcarb and compounds of the following formula
Figure imgf000030_0001
Figure imgf000030_0001
Aminoiso-thiazole der FormelAminoisothiazoles of the formula
Figure imgf000030_0002
Figure imgf000030_0002
worinwherein
R = -CH2O-CH3 oder H undR = -CH 2 O-CH 3 or H and
R' = -CF2CF2 CF3;R ' = -CF 2 CF 2 CF 3 ;
Anthranilamide der FormelAnthranilamide of the formula
Figure imgf000030_0003
worin R für Cι-C4-Alkyl wie Methyl, Ethyl, Isopropyl oder n-Butyl steht, und die Verbindung der folgenden Formel
Figure imgf000030_0003
wherein R is C 1 -C 4 -alkyl, such as methyl, ethyl, isopropyl or n-butyl, and the compound of the following formula
Figure imgf000031_0001
Figure imgf000031_0001
N-Phenylsemicarbazone, wie sie in EP-A 462 456 durch die allgemeine Formel I beschrieben werden, insbesondere Verbindungen der allgemeinen Formel IVN-phenylsemicarbazones, as described in EP-A 462 456 by the general formula I, in particular compounds of the general formula IV
Figure imgf000031_0002
worin R 1 und R12 unabhängig voneinander für Wasserstoff, Halogen, CN, Cι-C -Alkyl, Cι-C4-Alkoxy, d-QrHaloalkyl oder C C4-Haloalkoxy stehen und R13 für d-C^AIkoxy, d-C4-Haloalkyl oder C C4-Haloalkoxy steht, z. B. Verbindung IV, worin R11 für 3-CF3 und R12 für 4-CN stehen und R13 4-OCF3 bedeutet (= Metaflumizone).
Figure imgf000031_0002
wherein R 1 and R 12 are independently hydrogen, halogen, CN, -CC alkyl, -CC 4 alkoxy, d-QrHaloalkyl or CC 4 -haloalkoxy and R 13 is dC ^ alkoxy, dC 4 haloalkyl or CC 4 haloalkoxy is, for. B. Compound IV wherein R 11 is 3-CF 3 and R 12 is 4-CN and R 13 is 4-OCF 3 (= metaflumizone).
Brauchbare Wachstumsregulatoren sind z.B. Chlormequat-chlorid, Mepiquatchlorid, Prohexadion-Calcium oder die die Gruppe der Gibberelline. Dazu gehören z. B. die Gibberelline GA^ GA3, GA4, GA5 und GA7 etc. und die entsprechenden exo-16,17- Dihydrogibberelline sowie die Derivate davon, z.B. die Ester mit CrC4-Carbonsäuren. Erfindungsgemäß bevorzugt ist das exo-16,17-Dihydro-GA5-13-acetat, weiterhinUseful growth regulators are, for example, chlormequat chloride, mepiquat chloride, prohexadione calcium or the group of gibberellins. These include z. Example, the gibberellin GA ^ GA 3 , GA 4 , GA 5 and GA 7, etc. and the corresponding exo-16,17-Dihydrogibberelline and the derivatives thereof, for example, the esters with CrC 4 carboxylic acids. Preferred according to the invention is the exo-16,17-dihydro-GA 5 -13-acetate, furthermore
1 -Naphthylacetamid, 1-Naphthylessigsäure, 2-Naphthyloxyessigsäure, 3-CPA, 4-CPA, An- cymidol, Anthrachinon, BAP, Butifos; Tribufos, Butralin, Chlorflurenol, Clofencet, Cyclanili- de, Daminozide, Dicamba, Dikegulac sodium, Dimethipin, Chlorfenethol, Etacelasil, Ethephon, Ethychlozate, Fenoprop, 2,4,5-TP, Fluoridamid, Flurprimidol, Flutriafol, Guaza- tin, Imazalil, Indolylbuttersäure, Indolylessigsäure, Karetazan, Kinetin, Lactidichlor-ethyl, Maleic hydrazide, Mefluidide, Naptalam, Paclobutrazole, Quinmerac, Sintofen, Tetcyclacis, Thidiazuron, Triiodobezoicacid, Triapenthenol, Triazethan, Tribufos, Trinexapac-ethyl und Uniconazole.1-naphthylacetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, 3-CPA, 4-CPA, ancymidol, anthraquinone, BAP, butifos; Tribufos, Butralin, Chlorofur- nol, Clofencet, Cyclanilide, Daminozide, Dicamba, Dikegulac sodium, Dimethipine, Chlorfenethol, Etacelasil, Ethephon, Ethychlozate, Fenoprop, 2,4,5-TP, Fluoridamide, Flurprimidol, Flutriafol, Guazatine, Imazalil , Indolylbutyric, indolylacetic, karetazan, kinetin, lactidichloroethyl, maleic hydrazide, mefluidide, naptalam, paclobutrazole, quinmerac, sintofen, tetcyclacis, thidiazuron, triiodobezoicacid, tri-penthenol, triazethane, tribufos, trinexapac-ethyl and uniconazole.
Eine bevorzugte Ausführungsform der Erfindung betrifft die Verwendung der erfindungsgemäßen amphiphilen Polymerzusammensetzungen zur Herstellung wässriger Wirkstoffzusammensetzungen von Fungiziden, insbesondere Strobilurinen, Azolen und 6-Aryltriazolo[1 ,5a]pyrimidinen, wie sie z.B. in WO 98/46608, WO 99/41255 oder WO 03/004465 jeweils durch die allgemeine Formel I beschrieben werden, insbesondere für Wirkstoffe der allgemeinen Formel V,A preferred embodiment of the invention relates to the use of the amphiphilic polymer compositions according to the invention for the preparation of aqueous Active substance compositions of fungicides, in particular strobilurins, azoles and 6-aryltriazolo [1, 5a] pyrimidines, as described, for example, in WO 98/46608, WO 99/41255 or WO 03/004465 in each case by the general formula I, in particular for active compounds of the general formula V,
Figure imgf000032_0001
worin:
Figure imgf000032_0001
wherein:
Rx für eine Gruppe NR14R15 steht, oder lineares oder verzweigtes C C8-Alkyl, das gegebenenfalls durch Halogen, OH, Cι-C4-Alkoxy, Phenyl oder C3-C6-Cycloalkyl substituiert ist, C2-C6-Alkenyl, C3-C6-Cycloalkyl, C3-C6-Cycloalkenyl, Phenyl oder Naphthyl, wobei die 4 zuletzt genannten Reste 1 , 2, 3 oder 4 Substituenten ausgewählt unter Halogen, OH, Cι-C4-Alkyl, d-C4-Halogenalkoxy, d-C -Alkoxy und CrC4-Halogenalkyl aufweisen können;R x is a group NR 14 R 15 , or linear or branched C 8 -alkyl which is optionally substituted by halogen, OH, C 1 -C 4 -alkoxy, phenyl or C 3 -C 6 -cycloalkyl, C 2 -C 6- alkenyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, phenyl or naphthyl, where the 4 last mentioned radicals 1, 2, 3 or 4 substituents selected from halogen, OH, -CC 4 alkyl , dC 4 -haloalkoxy, dC -alkoxy and CrC 4 -haloalkyl;
R14, R 5 unabhängig voneinander für Wasserstoff, Cι-C8-Alkyl, CrC8-Halogenalkyl, C3-Cι0-Cycloalkyl, C3-C6-Halogencycloalkyl, C2-C8-Alkenyl, C4-Cι0-Alkadienyl, C2-C8-Halogenalkenyl, C3-C6-Cyclo- alkenyl, C2-C8-Halogencycloalkenyl, C2-C8-Alkinyl, C2-C8-Halogenalkinyl oder C3-C6-Cycloalkinyl,R 14, R 5 independently of one another are hydrogen, C 8 alkyl, -C 8 -haloalkyl, C 3 -Cι 0 cycloalkyl, C 3 -C 6 halocycloalkyl, C 2 -C 8 alkenyl, C 4 -Cι 0- alkadienyl, C 2 -C 8 -haloalkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 8 -halocycloalkenyl, C 2 -C 8 -alkynyl, C 2 -C 8 -haloalkynyl or C 3 -C 6 -cycloalkynyl,
R14 und R15 zusammen mit dem Stickstoffatom, an das sie gebunden sind, fünf- bis achtgliedriges Heterocyclyl, welches über N gebunden ist und ein, zwei oder drei weitere Heteroatome aus der Gruppe O, N und S als Ring- glied enthalten und/oder einen oder mehrere Substituenten aus der Gruppe Halogen, Cι-C6-Alkyl, CrC6-Halogenalkyl, C2-C6-Alkenyl, C2-C6-Halogenalkenyl, Cι-C6-Alkoxy, d-C6-Halogenalkoxy, C3-C6-Alkenyloxy, C3-C6-Halogenalkenyloxy, (exo)-Cι-C6-Alkylen und Oxy-d-C3-alkylenoxy tragen kann; ausgewählt ist unter Halogen, Cyano, CrC6-Alkyl, d-C4-Halogenalkyl, d-Cβ-Alkoxy, d-C4-Halogenalkoxy und d-C6-Alkoxycarbonyl;R 14 and R 15, together with the nitrogen atom to which they are attached, are five- to eight-membered heterocyclyl which is bonded via N and contains one, two or three further heteroatoms from the group O, N and S as ring member and / or one or more substituents from the group halogen, Cι-C6 alkyl, -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, Cι-C6 alkoxy, dC 6 haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 haloalkenyloxy, (exo) -Cι-C 6 alkylene and oxy-dC can carry 3 -alkylenoxy; is selected from halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 4 -haloalkoxy and C 1 -C 6 -alkoxycarbonyl;
L1 Halogen, d-C6-Alkyl oder d-C6-Halogenalkyl und insbesondere Fluor oder Chlor bedeutet; für Halogen, Cι-C4-Alkyl, Cyano, d-C4-Alkoxy oder C C4-Halogenalkyl und vorzugsweise für Halogen oder Methyl steht und insbesondere Chlor bedeutet.L 1 is halogen, dC 6 alkyl or dC 6 haloalkyl and in particular fluorine or chlorine; is halogen, C 1 -C 4 -alkyl, cyano, C 1 -C 4 -alkoxy or CC 4 -haloalkyl and preferably represents halogen or methyl and in particular chlorine.
Beispiele ür Verbindungen der Formel V sindExamples of compounds of the formula V are
5-Chlor-7 4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7 4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7 4-methylpiperazin-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7 4-methylpiperazin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7 morpholin-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7-morpholin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7 piperidin-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7 morpholin-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7-morpholin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7 isopropylamino)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7-isopropylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7 cyclopentylamino)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7-cyclopentylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7 2,2,2-trifluorethylamino)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 I5- ajpyrimidin5-chloro-7,2,2,2-trifluoroethylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1 I- ajpyrimidine
5-Chlor-7 1 ,1 ,1-trifluorpropan-2-ylamino)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5- ajpyrimidin5-chloro-7,1,1-trifluoropropan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-ajpyrimidine
5-Chlor-7 3,3-dimethylbutan-2-ylamino)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5- ajpyrimidin5-chloro-7,3,3-dimethylbutan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-ajpyrimidine
5-Chlor-7- cyclohexylmethyl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7-cyclohexylmethyl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7- cyclohexyl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7-cyclohexyl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7- 2-methylbutan-3-yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7- (2-methylbutan-3-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7- 3-methylpropan-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7- (3-methylpropan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7- 4-methylcyclohexan-1 -yl)-6-(2,4,6-trif luorphenyl)-[1 ,2,4]triazolo[1 ,5- ajpyrimidir5-chloro-7-4-methylcyclohexan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-imipyrimidir
5-Chlor-7- hexan-3-yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7-hexan-3-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7- 2-methylbutan-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7- (2-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7- 3-methylbutan-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-chloro-7- (3-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Chlor-7- 1 -methylpropan-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin, 5-Methyl-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5- ajpyrimidin,5-chloro-7- (1-methylpropan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-ajpyrimidine,
5-Methyl-7-(4-methylpiperazin-1 -yl)-6-(2,4,6-thfluorphenyl)-[1 ,2,4]triazolo[1 ,5- ajpyrimidin,5-methyl-7- (4-methylpiperazin-1-yl) -6- (2,4,6-thfluorophenyl) - [1,2,4] triazolo [1,5-ajpyrimidine,
5-Methyl-7-(morpholin-1 -yl)-6-(2,4,6-trif luorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin, 5-Methyl-7-(piperidin-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin, 5-Methyl-7-(morpholin-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-aJpyrimidin, 5-Methyl-7-(isopropylamino)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin, 5-Methyl-7-(cyclopentylamino)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin, 5-Methyl-7-(2,2,2-trifluorethylamino)-6-(2,4,6-trifluorphenyl)-[1 )2,4]triazolo[1 ,5- ajpyrimidin, 5-Methyl-7-(1 ,1 ,1 -trifluorpropan-2-ylamino)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5- ajpyrimidin,5-Methyl-7- (morpholin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (morpholin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (isopropylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (cyclopentylamino) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1, 5-a] pyrimidine, 5-methyl-7- (2,2,2-trifluoroethylamino) -6- (2,4,6-trifluorophenyl) - [1 ) 2,4] triazolo [1,5-ajpyrimidine, 5 -Methyl 7- (1,1-trifluoropropan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5] ajpyrimidin,
5-Methyl-7-(3,3-dimethylbutan-2-ylamino)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5- ajpyrimidin,5-methyl-7- (3,3-dimethylbutan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-ajpyrimidine,
5-Methyl-7-(cyclohexylmethyl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin, 5-Methyl-7-(cyclohexyl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-Methyl-7- (cyclohexylmethyl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (cyclohexyl) -6 - (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Methyl-7-(2-methylbutan-3-yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin, 5-Methyl-7-(3-methylpropan-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin, 5-Methyl-7-(4-methylcyclohexan-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5- a]pyrimidin, 5-Methyl-7-(hexan-3-yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin,5-Methyl-7- (2-methylbutan-3-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7 - (3-methylpropan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (4-methylcyclohexane 1 -yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (hexan-3-yl) -6 - (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,
5-Methyl-7-(2-methylbutan-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin, 5-Methyl-7-(3-methylbutan-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidin und 5-Methyl-7-(1 -methylpropan-1 -yl)-6-(2,4,6-trifluorphenyl)-[1 ,2,4]triazolo[1 ,5- ajpyrimidin.5-Methyl-7- (2-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7 - (3-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine and 5-methyl-7- (1-methylpropane 1 -yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-ajpyrimidine.
Eine weitere bevorzugte Ausführungsform der Erfindung betrifft die Verwendung der erfindungsgemäßen amphiphilen Polymerzusammensetzungen zur Herstellung von Wirkstoffzusammensetzungen, insbesondere von wässrigen Wirkstoffzusammensetzungen von Insektiziden, insbesondere von Arylpyrrolen wie Chlorfenapyr, von Py- rethroiden wie Bifenthrin, Cyfluthrin, Cycloprothrin, Cypermethrin, Deltamethrin, Esfen- valerate, Ethofenprox, Fenpropathrin, Fenvalerate, Cyhalothrin, Lambda-Cyhalothrin, Permethrin, Silafluofen, Tau-Fluvalinate, Tefluthrin, Tralomethrin, alpha-Cypermethrin, Zeta-Cypermethrin und Permethrin, von Neonicotinoiden und von Semicarbazonen der Formel IV.A further preferred embodiment of the invention relates to the use of the amphiphilic polymer compositions according to the invention for preparing active ingredient compositions, in particular aqueous active ingredient compositions of insecticides, in particular arylpyrroles such as chlorfenapyr, of pyrethroids such as bifenthrin, cyfluthrin, cycloprothrin, cypermethrin, deltamethrin, esfen valerates, Etofenprox, fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalothrin, permethrin, silafluofen, tau-fluvalinate, tefluthrin, tralomethrin, alpha-cypermethrin, zeta-cypermethrin and permethrin, of neonicotinoids and of semicarbazones of formula IV.
Außerdem eignen sich die erfindungsgemäßen amphiphilen Polymerzusammensetzungen zur Herstellung wässriger Wirkstoffzusammensetzungen von pharmazeutischen Wirkstoffen und Pro-Drugs. Hierzu zählen Benzodiazepine, Antihypertensiva, Vitamine, Cytostatika - insbesondere Taxol, Anästhetika, Neuroleptika, Antidepressiva, Antibiotika, Antimykotika, Fungizide, Chemotherapeutika, Urologika, Thrombozyte- naggregationshemmer, Sulfonamide, Spasmolytika, Hormone, Immunglobuline, Sera, Schilddrüsentherapeutika, Psychopharmaka, Parkinsonmittel und andere Antihyperki- netika, Ophthalmika, Neuropathiepräparate, Calciumstoffwechselregulatoren, Muskel- relaxantia, Narkosemittel, Lipidsenker, Lebertherapeutika, Koronarmittel, Kardiaka, Immuntherapeutika, regulatorische Peptide und ihre Hemmstoffe, Hypnotika, Sedativa, Gynäkologika, Gichtmittel, Fibrinolytika, Enzympräparate und Transportproteine, Enzyminhibitoren, Emetika, Durchblutungsfördemde Mittel, Diuretika, Diagnostika, Corti- coide, Cholinergika, Gallenwegstherapeutika, Antiasthmatika, Broncholytika, Betare- zeptorenblocker, Calciumantagonisten, ACE-Hemmer, Arteriosklerosemittel, Antiphlo- gistika, Antikoagulantia, Antihypotonika, Antihypoglykämika, Antihypertonika, Antifibri- nolytika, Antiepileptika, Antiemetika, Antidota, Antidiabetika, Antiarrhythmika, Antianä- mika, Antiallergika, Anthelmintika, Analgetika, Analeptika, Aldosteronantagonisten, Abmagerungsmittel. Beispiele für geeignete pharmazeutische Wirkstoffe sind die insbesondere die in den Absätzen 0105 bis 0131 der US 2003/0157170 genannten Wirk- Stoffe.In addition, the amphiphilic polymer compositions according to the invention are suitable for the preparation of aqueous active substance compositions of pharmaceutical active ingredients and prodrugs. These include benzodiazepines, antihypertensives, vitamins, cytostatic drugs - especially taxol, anesthetics, neuroleptics, antidepressants, antibiotics, antifungals, fungicides, chemotherapeutics, urologics, antiplatelet agents, sulfa drugs, spasmolytics, hormones, immunoglobulins, sera, thyroid drugs, psychotropic drugs, Parkinson's drugs and others Anti-hyperkinetics, ophthalmics, neuropathy preparations, calcium metabolism regulators, muscle relaxants, anesthetics, lipid-lowering agents, liver therapeutics, coronary agents, cardiacs, immunotherapeutics, regulatory peptides and their inhibitors, hypnotics, sedatives, gynecologics, gout, fibrinolytics, enzyme preparations and transport proteins, enzyme inhibitors, emetics, Circulation-promoting agents, diuretics, diagnostic agents, corticosteroids, cholinergics, biliary tract therapeutics, antiasthmatics, broncholytics, beta-adrenoceptors, calcium antagonists, ACE inhibitors, arteriosclerotic agents, antiphlogistics, anticoagulants, anti- hypotension, antihypoglycaemic, antihypertensive, antifibri- nolytics, antiepileptics, antiemetics, antidotes, antidiabetics, antiarrhythmics, antianemics, antiallergics, anthelmintics, analgesics, analeptics, aldosterone antagonists, weight loss agents. Examples of suitable active pharmaceutical ingredients are in particular the active substances mentioned in paragraphs 0105 to 0131 of US 2003/0157170.
Weiterhin eignen sich die erfindungsgemäßen amphiphilen Polymerzusammensetzungen zur Herstellung wässriger Zubereitungen von kosmetischen Wirkstoffen, insbesondere von kosmetischen Öle und Fetten wie Erdnussöl, Jojobaöl, Kokosnussöl, Mandelöl, Olivenöl, Palmöl, Ricinusöl, Sojaöl oder Weizenkeimöl, etherische Öle wie Latschenkiefernöl, Lavendelöl, Rosmarinöl, Fichtennadelöl, Kiefernnadelöl, Eukalyptusöl, Pfefferminzöl, Salbeiöl, Bergamottöl, Terpentinöl, Melissenöl, Wacholderöl, Zitronenöl, Anisöl, Kardamonöl, Campheröl etc. oder für Mischungen aus diesen Ölen.Furthermore, the amphiphilic polymer compositions according to the invention are suitable for the preparation of aqueous preparations of cosmetic active ingredients, especially of cosmetic oils and fats such as peanut oil, jojoba oil, coconut oil, almond oil, olive oil, palm oil, castor oil, soybean oil or wheat germ oil, essential oils such as mountain pine oil, lavender oil, rosemary oil, pine needle oil , Pine oil, eucalyptus oil, peppermint oil, sage oil, bergamot oil, turpentine oil, lemon balm oil, juniper oil, lemon oil, aniseed oil, cardamom oil, camphor oil etc. or for mixtures of these oils.
Außerdem eignen sich die erfindungsgemäßen amphiphilen Polymerzusammensetzungen zur Herstellung von Zubereitungen, insbesondere von wässrigen Zubereitungen von Nahrungsergänzungsmitteln wie wasserunlöslichen Vitaminen und Provitaminen wie Vitamin A, Vitamin A-Acetat, Vitamin D, Vitamin E, Tocopherol-Derivate wie Tocopherolacetat und Vitamin K.In addition, the amphiphilic polymer compositions according to the invention are suitable for the preparation of preparations, in particular of aqueous preparations of food supplements such as water-insoluble vitamins and provitamins such as vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherol derivatives such as tocopherol acetate and vitamin K.
Beispiele für Effektstoffe, die als erfindungsgemäße Wirkstoffzusammensetzung formuliert werden können, sind:Examples of effect substances which can be formulated as active substance composition according to the invention are:
Farbstoffe: z. B. die in DE-A 10245209 beschriebenen Farbstoffe sowie die gemäß Colour-Index als Disperse-Farbstoffe und als Solvent- Farbstoffe bezeichneten Verbindungen, die auch als Dispersionsfarbstoffe bezeichnet werden. Eine Zusammenstellung geeigneter Dispersionsfarbstoffe findet sich beispielsweise in Ulimanns Enzyklopädie der technischen Chemie, 4. Auflage, Bd. 10, S. 155-165 (siehe auch Bd. 7, S. 585ff - Anthrachinonfarbstoffe; Bd. 8, S. 244ff - Azofarbstoffe; Bd. 9, S. 313ff - Chi- nophthalonfarbstoffe). Auf diese Literaturstelle und die darin genannten Verbindungen wird hiermit ausdrücklich Bezug genommen. Erfindungsgemäß geeignete Dispersionsfarbstoffe und Solvent-Farbstoffe umfassen verschiedenste Farbstoffklassen mit unterschiedlichen Chromophoren, beispielsweise Anthrachinonfarbstoffe, Monoazo- und Disazofarbstoffe, Chinophthalone, Methin- und Azamethinfarbstoffe, Naphthalimid- farbstoffe, Naphthochinonfarbstoffe und Nitrofarbstoffe. Beispiele für erfindungsgemäß geeignete Dispersionsfarbstoffe sind die Dispersionsfarbstoffe der folgenden Colour- Index Liste: C. I. Disperse Yellow 1 - 228, C. I. Disperse Orange 1 - 148, C. I. Disperse Red 1 - 349, C. I. Disperse Violet 1 - 97, C. I. Disperse Blue 1 - 349, C. I. Disperse Green 1 - 9, C. I. Disperse Brown 1 - 21 , C. I. Disperse Black 1 - 36. Beispiele für erfin- dungsgemäß geeignete Solvent-Farbstoffe sind die Verbindungen der folgenden Co- lour-lndex Liste: C. I. Solvent Yellow 2 - 191 , C. I. Solvent Orange 1 - 113, C. I. Solvent Red 1 - 248, C. I. Solvent Violet 2 - 61 , C. I. Solvent Blue 2 - 143, C. I. Solvent Green 1 - 35, C. I. Solvent Brown 1 - 63, C. I. Solvent Black 3 - 50. Erfindungsgemäß geeignete Farbstoffe sind weiterhin Derivate des Naphthalins, des Anthracens, des Perylens, des Terylens, des Quarterylens, sowie Diketopyrrolopyrrolfarbstoffe, Perinonfarbstoffe, Cumarinfarbstoffe, Isoindolin- und Isoindolinonfarbstoffe, Porphyrinfarbstoffe, Phthalo- cyanin- und Naphthalocyaninfarbstoffe; undDyes: z. For example, the dyes described in DE-A 10245209 and the color Index referred to as a disperse dyes and as solvent dyes compounds, which are also referred to as disperse dyes. A compilation of suitable disperse dyes can be found, for example, in Ulimanns Enzyklopadie der technischen Chemie, 4th Edition, Vol. 10, pp. 155-165 (see also Vol. 7, pp. 585ff - anthraquinone dyes; Vol. 8, pp. 244ff - azo dyes; Vol. 9, p. 313ff - quinophthalone dyes). This reference and the compounds mentioned therein are hereby incorporated by reference. Disperse dyes and solvent dyes which are suitable according to the invention comprise a wide variety of dye classes with different chromophores, for example anthraquinone dyes, monoazo and disazo dyes, quinophthalones, methine and azamethine dyes, naphthalimide dyes, naphthoquinone dyes and nitro dyes. Examples of disperse dyes which are suitable according to the invention are the disperse dyes of the following color index list: CI Disperse Yellow 1 - 228, CI Disperse Orange 1 - 148, CI Disperse Red 1 - 349, CI Disperse Violet 1 - 97, CI Disperse Blue 1 - 349, CI Disperse Green 1 - 9, CI Disperse Brown 1 - 21, CI Disperse Black 1 - 36. Examples of solvent dyes suitable according to the invention are the compounds of the following co-solvents. lour Index List: CI Solvent Yellow 2 - 191, CI Solvent Orange 1 - 113, CI Solvent Red 1 - 248, CI Solvent Violet 2 - 61, CI Solvent Blue 2 - 143, CI Solvent Green 1 - 35, CI Solvent Brown 1 to 63, CI Solvent Black 3 to 50. Dyes which are also suitable according to the invention are derivatives of naphthalene, of anthracene, of perylene, of terylene, of quarterylene and of diketopyrrolopyrrole dyes, perinone dyes, coumarin dyes, isoindoline and isoindolinone dyes, porphyrin dyes, phthalocyanine. and naphthalocyanine dyes; and
UV-Absorber: insbesondere Verbindungen aus den nachfolgend genannten Gruppen a bis gUV absorbers: in particular compounds from groups a to g below
a) 4,4-Diarylbutadiene, b) Zimtsäureester, c) Benzotriazole, d) Hydroxybenzophenone, e) Diphenylcyanacrylate, f) Oxamide, g) 2-Phenyl-1 ,3,5-triazine;a) 4,4-diarylbutadienes, b) cinnamic acid esters, c) benzotriazoles, d) hydroxybenzophenones, e) diphenylcyanoacrylates, f) oxamides, g) 2-phenyl-1,3,5-triazines;
Zur Gruppe a) der 4,4-Diarylbutadiene zählen beispielsweise Verbindungen der Formel A.The group a) of the 4,4-diarylbutadienes include, for example, compounds of the formula A.
Figure imgf000036_0001
Figure imgf000036_0001
Die Verbindungen sind aus der EP-A-916 335 bekannt. Die Substituenten R10 und/oder Rn bedeuten bevorzugt C C8-Alkyl und C5-C8-Cycloalkyl.The compounds are known from EP-A-916 335. The substituents R 10 and / or Rn are preferably CC 8 -alkyl and C 5 -C 8 -cycloalkyl.
Zur Gruppe b) der Zimtsäureester zählen beispielsweise 4-Methoxyzimtsäure-2- isoamylester, 4-Methoxyzimtsäure-2-ethylhexylester, Methyl-α-methoxycarbonyl- cinnamat, Methyl-α-cyano-ß-methyl-p-methoxycinnamat, Butyl-α-cyano-ß-methyl-p- methoxy-cinnamat und Methyl-α-methoxycarbonyl-p-methoxycinnamat.The group b) of cinnamic acid esters includes, for example, 2-isoamyl 4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methyl α-methoxycarbonyl cinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α- cyano-.beta.-methyl-p-methoxy-cinnamate and methyl-.alpha.-methoxycarbonyl-p-methoxycinnamate.
Zur Gruppe c) der Benzotriazole zählen beispielsweise 2-(2'-Hydroxyphenyl)- benzotriazole wie 2-(2'-Hydroxy-5'-methylphenyl)-benzotriazol, 2-(3',5'-Di-tert-butyl-2'- hydroxyphenyl)benzotriazol, 2-(5'-tert-Butyl-2,-hydroxyphenyl)-benzotriazol, 2-(2'-Hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazol, 2-(3',5'-Di-tert-butyl-2'- hydroxyphenyl)-5-chlor-benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5,-methylphenyl)-5- chlor-benzotriazol, 2-(3'-sec-Butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazol, 2-(2'-Hydroxy-4,-octyloxyphenyl)-benzotriazol, 2-(3\5'-Di-tert-amyl-2'-hydroxyphenyl)- benzotriazol, 2-(3',5'-Bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazol, 2-(3'-tert-Butyl-2,-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlor-benzotriazol, 2-(3'-tert-Butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chlor- benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlor- benzotriazol, 2-(3'-tert-Butyl-2,-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)- benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)- benzotriazol, 2-(3'-tert-Butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)- benzotriazol, 2-(3'-Dodecyl-2'-hydroxy-5'-methylphenyl)-benzotriazol und 2-(3'-tert- Butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)-phenylbenzotriazol, 2,2'-Methylen- bis[4-(1 ,1 ,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-phenol]; das Produkt der Vereste- rung von 2-[3'-tert-Butyl-5'-(2-methoxycarbonylethyl)-2,-hydroxyphenyl]-2H-benzotriazol mit Polyethylenglycol 300; [R-CH2CH2-COO(CH2)3]2> mit R = 3'-tert-Butyl-4'-hydroxy-5'- 2H-benzotriazol-2-yl-phenyl und Gemische davon.The group c) of the benzotriazoles includes, for example, 2- (2'-hydroxyphenyl) benzotriazoles, such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl- 2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2 , -hydroxyphenyl) -benzotriazole, 2- (2'-Hydroxy-5 '- (1, 1, 3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 , -methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'- hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4 , octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5 Bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2 , -hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2 '-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2 , -hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2 - (3'-tert-Butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] 2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotr iazole and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) -phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol]; the product of the esterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2 , -hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH 2 CH 2 -COO (CH 2 ) 3 ] 2> with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl and mixtures thereof.
Zur Gruppe d) der Hydroxybenzophenone zählen beispielsweise 2-Hydroxybenzophenone wie 2-Hydroxy-4-methoxybenzophenon, 2,2'-Dihydroxy-4- methoxybenzophenon, 2,4-Dihydroxybenzophenon, 2,2',4,4'-Tetrahydroxybenzo- phenon, 2,2'-Dihydroxy-4,4,-dimethoxybenzophenon, 2,2'-Dihydroxy-4,4'-dimethoxy- benzophenon, 2-Hydroxy-4-(2-ethylhexyloxy)benzophenon, 2-Hydroxy-4-(n-octyl- oxy)benzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon, 2-Hydroxy-3- carboxybenzophenon, 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure und derenExamples of groups d) of hydroxybenzophenones include 2-hydroxybenzophenones, such as 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzo-phenone , 2,2'-dihydroxy-4,4, -dimethoxybenzophenon, 2,2'-dihydroxy-4,4'-dimethoxy benzophenone, 2-hydroxy-4- (2-ethylhexyloxy) benzophenone, 2-hydroxy-4- (n-octyl-oxy) benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-3-carboxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and their
Natriumsalz, 2,2'-Dihydroxy-4,4'-dimethoxybenzophenon-5,5'-bissulfonsäure und deren Natriumsalz.Sodium salt, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-bisulfonic acid and its sodium salt.
Zur Gruppe e) der Diphenylcyanacrylate zählen beispielsweise Ethyl-2-cyan-3,3- diphenylacrylat, das beispielsweise im Handel unter dem Namen Uvinul® 3035 der Fa. BASF AG, Ludwigshafen erhältlich ist, 2-Ethylhexyl-2-cyan-3,3-diphenylacrylat, das beispielsweise im Handel als Uvinul® 3039 der Fa. BASF AG, Ludwigshafen, erhältlich ist und 1 ,3-Bis-[(2'-cyano-3,,3'-diphenylacryloyl)oxy]-2,2-bis{[2,-cyano-3',3'-diphenyl- acryloyl)oxy]methyl}propan, das beispielsweise im Handel unter dem Namen Uvinul® 3030 der Fa. BASF AG, Ludwigshafen erhältlich ist.The group e) of the diphenylcyanoacrylates includes, for example, ethyl-2-cyano-3,3-diphenylacrylate, which is obtainable, for example, commercially under the name Uvinul® 3035 from BASF AG, Ludwigshafen, 2-ethylhexyl-2-cyano-3, 3-diphenyl acrylate, which is available commercially for example as Uvinul® 3039 from BASF AG, Ludwigshafen, Germany and 1, 3-bis -. [(2'-cyano-3, 3'-diphenylacryloyl) oxy] -2,2 bis {[2 , cyano-3 ', 3'-diphenyl-acryloyl) oxy] methyl} propane, which is commercially available, for example, under the name Uvinul® 3030 from BASF AG, Ludwigshafen.
Zur Gruppe f) der Oxamide zählen beispielsweise 4,4'-Dioctyloxyoxanilid, 2,2'-Di- ethoxyoxanilid, 2,2'-Dioctyloxy-5,5'-di-tert-butoxanilid, 2,2'-Didodecyloxy-5,5'-di-tert- butoxanilid, 2-Ethoxy-2'-ethyloxanilid, N,N'-Bis(3-dimethylaminopropyl)oxamid, 2- Ethoxy-5-tert-butyl-2'-ethoxanilid und dessen Mischung mit 2-Ethoxy-2'-ethyl-5,4'-di- tert-butoxanilid sowie Mischungen von ortho-, para-Methoxy-disubstituierten Oxaniliden und Mischungen von ortho- und para-Ethoxy disubstituierten Oxaniliden.The group f) of the oxamides includes, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5 , 5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di- tert-butoxanilide and mixtures of ortho-, para-methoxy-disubstituted oxanilides and mixtures of ortho and para-ethoxy disubstituted oxanilides.
Zur Gruppe g) der 2-Phenyl-1 ,3,5-triazine zählen beispielsweise 2-(2-Hydroxyphenyl)- 1 ,3,5-triazine wie 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1 ,3,5-triazin, 2-(2-Hydroxy-4- octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazin, 2-(2,4-Dihydroxyphenyl)-4,6- bis(2,4-dimethylphenyl)-1 ,3,5-triazin, 2,4-Bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4- dimethylphenyl)-1 ,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)- 1 ,3,5-triazin, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5- triazin, 2-(2-Hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazin, 2- [2-Hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)-phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5- triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-octyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)- 1 ,3,5-triazin, 2-[4-(Dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6- bis(2,4-dimethylphenyl)-1 ,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-dodecyloxy- propoxy)phenyl]-4,6-bis-(2,4-dimethylphenyl)-1 ,3,5-triazin, 2-(2-Hydroxy-4- hexyloxyphenyl)-4,6-diphenyl-1 ,3,5-triazin, 2-(2-Hydroxy-4-methoxyphenyl)-4,6- diphenyl-1 ,3,5-triazin, 2,4,6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]- 1 ,3,5-triazin und 2-(2-Hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1 ,3,5-triazin.Group g) of 2-phenyl-1,3,5-triazines includes, for example, 2- (2-hydroxyphenyl) -1,3,5-triazines such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2,4-dihydroxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4 , 6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3.5 triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propoxy) -phenyl] -4,6-bis (2,4-dimethyl) -1, 3,5-triazine, 2- [2-Hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy) tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3 -dodecyloxypropoxy) phenyl] -4,6-bis- (2,4-dimethylphenyl) -1,3,5- triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3, 5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine and 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine.
Neben den vorgenannten Bestandteilen können die erfindungsgemäßen wässrigen Wirkstoffzusammensetzungen auch konventionelle oberflächenaktive Substanzen und sonstige Additive enthalten. Zu den oberflächenaktiven Substanzen zählen Tenside, Dispergierhilfsmittel und Netzmittel. Zu den sonstigen Additiven zählen insbesondere Verdickungsmittel, Entschäumer, Konservierungsmittel, Frostschutzmittel Stabilisie- rungsmittel, etc.In addition to the abovementioned constituents, the aqueous active substance compositions according to the invention may also contain conventional surface-active substances and other additives. Surfactants include surfactants, dispersing aids and wetting agents. The other additives include in particular thickeners, defoamers, preservatives, antifreeze stabilizers, etc.
Prinzipiell brauchbar sind anionische, kationische, nichtionische und amphotere Tenside, wobei Polymer-Tenside sowie Tenside mit Heteroatomen in der hydrophoben Gruppe eingeschlossen sind.In principle, anionic, cationic, nonionic and amphoteric surfactants are usable, wherein polymer surfactants and surfactants with heteroatoms are included in the hydrophobic group.
Zu den anionischen Tensiden gehören beispielsweise Carboxylate, insbesondere Alkali-, Erdalkali- und Ammoniumsalze von Fettsäuren, z. B. Kaliumstearat, die üblicherweise auch als Seifen bezeichnet werden; Acylglutamate; Sarkosinate, z. B. Natrium- lauroylsarkosinat; Taurate; Methylcellulosen; Alkylphosphate, insbesondere Mono- und Diphosphorsäurealkylester; Sulfate, insbesondere Alkylsulfate und Alkylethersulfate; Sulfonate, weitere Alkyl- und Alkylarylsulfonate, insbesondere Alkali-, Erdalkali- und Ammoniumsalze von Arylsulfonsäuren sowie alkylsubstituierten Arylsulfonsäuren, Al- kylbenzolsulfonsäuren, wie beispielsweise Lignin- und Phenolsulfonsäure, Naphthalin- und Dibutylnaphthalinsulfonsäuren, oder Dodecylbenzolsulfonate, Alkylnaphthalinsul- fonate, Alkylmethylestersulfonate, Kondensationsprodukte von sulfoniertem Naphthalin und Derivaten davon mit Formaldehyd, Kondensationsprodukte von Naphthalinsulfon- säuren, Phenol- und/oder Phenolsulfonsäuren mit Formaldehyd oder mit Formaldehyl und Harnstoff, Mono- oder Dialkyl-bemsteinsäureestersulfonate; sowie Eiweißhydroly- sate und Lignin-Sulfitablaugen. Die zuvor genannten Sulfonsäuren werden vorteilhaft- erweise in Form ihrer neutralen oder gegebenenfalls basischen Salze verwendet.The anionic surfactants include, for example, carboxylates, especially alkali, alkaline earth and ammonium salts of fatty acids, eg. B. potassium stearate, which are commonly referred to as soaps; glutamates; Sarcosinates, e.g. For example, sodium lauroyl sarcosinate; taurates; Methylcelluloses; Alkyl phosphates, especially mono- and diphosphoric acid alkyl esters; Sulfates, in particular alkyl sulfates and alkyl ether sulfates; Sulphonates, other alkyl and alkylarylsulphonates, in particular alkali, alkaline earth and ammonium salts of arylsulfonic acids and alkyl-substituted arylsulfonic acids, alkylbenzenesulfonic acids, such as lignin and phenolsulfonic acid, naphthalene and dibutylnaphthalenesulfonic acids, or dodecylbenzenesulfonates, alkylnaphthalenesulfonates, alkylmethylsulfonates, condensation products of sulfonated naphthalene and derivatives thereof with formaldehyde, condensation products of naphthalenesulfonic acids, phenol- and / or phenolsulfonic acids with formaldehyde or with formaldehyl and urea, mono- or dialkylsuccinic acid sulfonates; as well as protein hydrolysates and lignin sulphite waste liquors. The abovementioned sulfonic acids are advantageously used in the form of their neutral or optionally basic salts.
Zu den kationischen Tensiden gehören beispielsweise quaternierte Ammoniumverbindungen, insbesondere Alkyltrimethylammonium- und Dialkyldimethylammonium- Halogenide und -alkylsulfate sowie Pyridin- und Imidazolin-Derivate, insbesondere Al- kylpyridinium-Halogenide.The cationic surfactants include, for example, quaternized ammonium compounds, in particular alkyltrimethylammonium and dialkyldimethylammonium halides and alkylsulfates, and also pyridine and imidazoline derivatives, in particular alkylpyridinium halides.
Zu den nichtionischen Tensiden gehören beispielsweise:Nonionic surfactants include, for example:
Fettalkoholpolyoxyethylenester, beispielsweise Laurylalkohol- polyoxyethylenetheracetat, Alkyl-Polyoxyethylen- und -polyoxypropylen-ether, z. B. von iso-Tridecylalkohol und Fettalkohol-Polyoxyethylenether, Alkylarylalkohol-Polyoxyethylenether, z. B. Octylphenol-Polyoxyethylenether, alkoxylierte tierische und/oder pflanzliche Fette und/oder Öle, beispielsweise Maisölethoxylate, Rizinusölethoxylate, Talgfettethoxylate, Glycerinester, wie beispielsweise Glycerinmonostearat, Fettalkoholalkoxylate und Oxoalkoholalkoxylate, insbesondere vom Typ RO-(Rι8O)r(R19O)sR2o mit R18 und R-,9 unabhängig voneinander = C2H4, C3H6) C4H8 und R20 = H, oder d-C12-Alkyl, R = C3-C30-Alkyl oder C6-C30-Alkenyl, r und s unabhängig voneinander 0 bis 50, wobei nicht beide für 0 stehen können, wie iso-Tridecylalkohol und Oleylalkohol-polyoxyethylenether, Alkylphenolalkoxylate, wie beispielsweise ethoxyliertes iso-Octyl-, Octyl- oder Nonyl-phenol, Tributylphenol-polyoxyethylenether, Fettaminalkoxylate, Fettsäureamid- und Fettsäurediethanol-amidalkoxylate, ins- besondere deren Ethoxylate, Zuckertenside, Sorbitester, wie beispielsweise Sorbitanfettsäureester (Sorbitan- monooleat, Sorbitantristearat), Polyoxy-ethylensorbitanfettsäureester, Alkylpo- lyglycoside, N-Alkylgluconamide, Alkylmethylsulfoxide, - Alkyldimethylphosphinoxide, wie beispielsweise Tetradecyldimethylphosphinoxid.Fatty alcohol polyoxyethylene esters, for example, lauryl alcohol polyoxyethylene ether acetate, alkyl polyoxyethylene and polyoxypropylene ethers, e.g. For example, iso-tridecyl alcohol and fatty alcohol polyoxyethylene ethers, alkylaryl alcohol polyoxyethylene ethers, e.g. For example, octylphenol polyoxyethylene ethers, alkoxylated animal and / or vegetable fats and / or oils, for example corn oil ethoxylates, castor oil ethoxylates, tallow fatty ethoxylates, glycerol esters, such as glycerol monostearate, fatty alcohol alkoxylates and Oxoalkoholalkoxylate, in particular of the type RO- (Rι 8 O) r (R 19 O ) s R2o with R 18 and R-, 9 independently of one another = C 2 H 4 , C 3 H 6) C 4 H 8 and R 20 = H, or C 1 -C 12 -alkyl, R = C 3 -C 30 -alkyl or C 6 -C 30 alkenyl, r and s are each independently 0 to 50, both of which can not be 0, such as iso-tridecyl alcohol and oleyl alcohol polyoxyethylene ethers, alkylphenol alkoxylates such as ethoxylated iso-octyl, octyl or nonyl-phenol , Tributylphenol polyoxyethylene ethers, fatty amine alkoxylates, fatty acid amide and fatty acid diethanol amide alkoxylates, in particular their ethoxylates, sugar surfactants, sorbitol esters, such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbi tan fatty acid esters, alkyl polyglycosides, N-alkylgluconamides, alkylmethylsulfoxides, alkyldimethylphosphine oxides, such as, for example, tetradecyldimethylphosphine oxide.
Zu den amphoteren Tensiden gehören beispielsweise Sulfobetaine, Carboxybetaine und Alkyldimethylaminoxide, z. B. Tetradecyldimethylaminoxid. Weitere Tenside, die hier beispielhaft genannt werden sollen, sind Perfluortenside, Silikontenside, Phospholipide, wie beispielsweise Lecithin oder chemisch modifizierte Lecithine, Aminosäuretenside, z. B. N-Lauroylglutamat.The amphoteric surfactants include, for example, sulfobetaines, carboxybetaines and alkyldimethylamine oxides, e.g. B. tetradecyldimethylamine oxide. Other surfactants which are to be mentioned here by way of example are perfluorosurfactants, silicone surfactants, phospholipids, such as lecithin or chemically modified lecithins, amino acid surfactants, eg. B. N-lauroylglutamate.
Sofern nicht spezifiziert, handelt es sich bei den Alkylketten der oben aufgeführten Tenside um lineare oder verzweigte Reste mit üblicherweise 8 bis 20 Kohlenstoffatomen.Unless specified, the alkyl chains of the surfactants listed above are linear or branched radicals of usually 8 to 20 carbon atoms.
In einer Ausführungsform enthalten die erfindungsgemäßen wässrigen Wirkstoffzu- sammensetzung nicht mehr als 10 Gew.-%, vorzugsweise nicht mehr als 5 Gew.-% und insbesondere nicht mehr als 3 Gew.-%, z.B. 0,01 bis 5 Gew.-% oder 0,1 bis 3 Gew.-% an konventionellen oberflächenaktiven Substanzen, jeweils bezogen auf die Gesamtmenge an Wirkstoff und Polymerzusammensetzung. Die konventionellen oberflächenaktiven Substanzen machen dann vorzugsweise nicht mehr als 5 Gew.-% und insbesondere nicht mehr als 3 Gew.-%, z.B. 0,01 bis 5 Gew.-% oder 0,1 bis 3 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung aus.In one embodiment, the aqueous active ingredient composition according to the invention contains not more than 10% by weight, preferably not more than 5% by weight and in particular not more than 3% by weight, e.g. 0.01 to 5 wt .-% or 0.1 to 3 wt .-% of conventional surface-active substances, each based on the total amount of active ingredient and polymer composition. The conventional surfactants then preferably make no more than 5% by weight, and more preferably not more than 3% by weight, e.g. 0.01 to 5 wt .-% or 0.1 to 3 wt .-%, based on the total weight of the composition of.
Je nach Anwendung kann es jedoch von Vorteil sein, wenn die erfindungsgemäßen Wirkstoffzusammensetzungen mit oberflächenaktiven Substanzen formuliert werden. Dann liegt der Anteil an konventioneller oberflächenaktiver Substanz häufig im Bereich von 0,5 bis 30 Gew.-%, insbesondere im Bereich von 1 bis 20 Gew.-%, bezogen auf die Gesamtmenge an Wirkstoff und Polymerzusammensetzung, bzw. im Bereich von 0,2 bis 20 Gew.-% und insbesondere im Bereich von 0,5 bis 15 Gew.-%, bezogen auf das Gesamtgewicht der formulierten Zusammensetzung.Depending on the application, however, it may be advantageous if the active substance compositions according to the invention are formulated with surface-active substances. Then, the proportion of conventional surface-active substance is often in the range of 0.5 to 30 wt .-%, in particular in the range of 1 to 20 wt .-%, based on the total amount of active ingredient and polymer composition, or in the range of 0, From 2 to 20% by weight and in particular from 0.5 to 15% by weight, based on the total weight of the formulated composition.
Auch wenn ein Vorteil der erfindungsgemäßen Zusammensetzungen ihr geringer Gehalt an flüchtigen organischen Substanzen ist, kann es für einige Anwendungen erwünscht sein, die erfindungsgemäßen Zusammensetzungen mit organischen Lösungsmitteln, Ölen und Fetten, vorzugsweise solchen Lösungsmitteln oder Ölen und Fetten, die umweltverträglich oder biokompatibel sind, z. B. die vorgenannten mit Wasser mischbaren Lösungsmittel oder Lösungsmittel, Ölen oder Fetten die mit Wasser nicht oder nur sehr begrenzt mischbar sind, zu mischen z. B. mit:Although an advantage of the compositions of the present invention is their low volatile organic content, for some applications it may be desirable to include the compositions of the present invention with organic solvents, oils and fats, preferably such solvents or oils and fats that are environmentally or biocompatible, e.g. , As the aforementioned water-miscible solvents or solvents, oils or fats which are not or only to a limited extent miscible with water, to mix z. With:
Parrafinöle, aromatische Kohlenwasserstoffe und aromatische Kohlenwasser- stoffgemische, z. B. Xylole, Solvesso 100, 150 oder 200, und dergleichen, Phenole und Alkylphenole, z. B. Phenol, Hydrochinon, Nonylphenol, etc. Ketone mit mehr als 4 C-Atomen wie Cyclohexanon, Isophoron, Isopheron, Ace- tophenon, Acetonaphthon, Alkohole mit mehr als 4 C-Atomen wie acetylierter Lanolinalkohol, Cetylalkohol, 1 -Decanol, 1 -Heptanol, 1 -Hexanol, Isooctadecanol, Isopropylalkohol, Oleylalko- hol, Benzylalkohol, Carbonsäureester, z. B. Adipinsäuredialkylester wie Adipinsäurebis(2- ethylhexyl)ester, Phthalsäuredialkylester wie Phthalsäurebis(2-ethylhexyl)ester, Essigsäurealkylester (auch verzweigte Alkylgruppen) wie Ethylacetat und Ace- toessigsäureethylester, Stearate wie Butylstearat, Glycerinmonostearat, Citrate wie Acetyltributylcitrat, weiterhin Cetyloctanoat, Methyloleat, Methyl-p- hydroxyvbenzoat, Methyltetradecanoat, Propyl-p-hydroxybenzoat, Methylbenzo- at, Milchsäureester wie Isopropyllacttat, Butyllactat und 2-Ethylhexyllactat, Pflanzenöle wie Palmöl, Rapsöl, Rizinusöl und Derivate davon wie z. B. oxydiert, Kokusnussöl, Lebertran, Maiskeimöl, Sojabohnenöl, Leinsamenöl, Olivenöl, Erd- nussöl, Färberdistelöl, Sesamsamenöl, Grapefruitöl, Basilikumöl, Aprikosenöl, Ingweröl, Geranienöl, Orangenöl, Rosmarienöl, Macadamiaöl, Zwiebelöl, Manda- rinenöl, Kiefemöl, Sonnenblumenöl, hydrogenierte Pflanzenöle wie hydrogeniertes Palmöl, hydrogeniertes Rapsöl, hydrogeniertes Sojabohnenöl, tierische Öle wie Schweinefettöl, Fischöle, Dialkylamide mittet bis langkettiger Fettsäuren z. B. Hallcomide sowie - Pflanzenölester wie Rapsölmethylester.Parrafin oils, aromatic hydrocarbons and aromatic hydrocarbon mixtures, eg. Xylenes, Solvesso 100, 150 or 200, and the like, phenols and alkylphenols, e.g. Phenol, hydroquinone, nonylphenol, etc. ketones having more than 4 C atoms such as cyclohexanone, isophorone, isopherone, acetophenone, acetonaphthone, Alcohols having more than 4 C atoms, such as acetylated lanolin alcohol, cetyl alcohol, 1-decanol, 1-heptanol, 1-hexanol, isooctadecanol, isopropyl alcohol, oleyl alcohol, benzyl alcohol, carboxylic esters, eg. B. dialkyl adipate such as adipic acid bis (2-ethylhexyl) ester, dialkyl phthalates such as phthalic acid bis (2-ethylhexyl) esters, alkyl acetates (also branched alkyl groups) such as ethyl acetate and acetoacetate, stearates such as butyl stearate, glycerol, citrates such as acetyltributyl citrate, further cetyloctanoate, methyl oleate, Methyl p-hydroxybenzoate, methyl tetradecanoate, propyl p-hydroxybenzoate, methylbenzoate, lactic acid esters such as isopropyl lactate, butyl lactate and 2-ethylhexyl lactate, vegetable oils such as palm oil, rapeseed oil, castor oil and derivatives thereof such as e.g. Oxygenated, coconut oil, cod liver oil, corn oil, soybean oil, linseed oil, olive oil, peanut oil, safflower oil, sesame seed oil, grapefruit oil, basil oil, apricot oil, ginger oil, geranium oil, orange oil, rosemary oil, macadamia oil, onion oil, mandarin oil, pine oil, sunflower oil, Hydrogenated vegetable oils such as hydrogenated palm oil, hydrogenated rapeseed oil, hydrogenated soybean oil, animal oils such as lard oil, fish oils, dialkylamides to long-chain fatty acids z. B. Hallcomide and - vegetable oil esters such as rapeseed oil methyl ester.
Geeignete Verdicker sind Verbindungen, die der Formulierung ein pseudoplastisches Fließverhalten verleihen, d.h. hohe Viskosität im Ruhezustand und niedrige Viskosität im bewegten Zustand. Hier sind beispielsweise Polysaccharide bzw. organische Schichtmineralien wie Xanthan Gum® (Kelzan® der Fa. Kelco), Rhodopol® 23 (Rhone Poulenc) oder Veegum® (Firma R.T. Vanderbilt) oder Attaclay® (Firma Engelhardt) zu nennen, wobei Xanthan-Gum® bevorzugt verwendet wird.Suitable thickeners are compounds which give the formulation a pseudoplastic flow behavior, ie high viscosity at rest and low viscosity in the agitated state. Here, for example, polysaccharides or organic layer minerals such as Xanthan Gum ® (Kelzan ® from. Kelco), Rhodopol ® 23 (Rhone Poulenc) or Veegum ® (from RT Vanderbilt) or Attaclay ® (Engelhardt) to call, said xanthan gum ® is preferably used.
Als für die erfindungsgemäßen Dispersionen geeignete Antischaummittel kommen bei- spielsweise Silikonemulsionen (wie z. B. Silikon® SRE, Firma Wacker oder Rhodorsil® der Firma Rhodia), langkettige Alkohole, Fettsäuren, fluororganische Verbindungen und deren Gemische in Betracht.As suitable for the dispersions according to the invention antifoams examples game, silicone emulsions (such as, for example, silicone ® SRE, from Wacker, or Rhodorsil ® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
Bakterizide können zur Stabilisierung den erfindungsgemäßen Zusammensetzungen gegen Befall mit Mikroorganismen zugesetzt werden. Geeignete Bakterizide sind beispielsweise Proxel® der Fa. ICI oder Acticide® RS der Fa. Thor Chemie und Kathon® MK der Firma Rohm & Haas. Geeignete Frostschutzmittel sind organische Polyole, z. B. Ethylenglycol, Propylengly- col oder Glycerin. Diese werden üblicherweise in Mengen von nicht mehr als 10 Gew.- %, bezogen auf das Gesamtgewicht der Wirkstoffzusammensetzung eingesetzt um den gewünschten Gehalt an flüchtigen Verbindungen nicht zu überschreiten. In einer Ausführungsform der Erfindung beträgt der Anteil hiervon verschiedener flüchtiger organischer Verbindungen vorzugsweise nicht mehr als 1 Gew.-%, insbesondere nicht mehr als 1000 ppm.Bactericides may be added to stabilize the compositions of the invention against attack by microorganisms. Suitable bactericides are, for example Proxel ® from. ICI or Acetide ® RS from. Thor Chemie and Kathon ® MK from Rohm & Haas. Suitable antifreeze are organic polyols, eg. As ethylene glycol, propylene glycol or glycerol. These are usually used in amounts of not more than 10% by weight, based on the total weight of the active ingredient composition, in order not to exceed the desired content of volatile compounds. In one embodiment of the invention, the proportion thereof of various volatile organic compounds is preferably not more than 1 wt .-%, in particular not more than 1000 ppm.
Gegebenenfalls können die erfindungsgemäßen Wirkstoffzusammensetzungen 1 bis 5 Gew.-% Puffer bezogen auf die Gesamtmenge der hergestellten Formulierung zur pH-Wert Regulation enthalten, wobei sich die Menge und Art des eingesetzten Puffers nach den chemischen Eigenschaften des Wirkstoffes bzw. der Wirkstoffe richtet. Beispiele für Puffer sind Alkalisalze schwacher anorganischer oder organischer Säuren wie z. B. Phosphorsäure, Borsäure, Essigsäure, Propionsäure, Citronensäure, Fumar- säure, Weinsäure, Oxalsäure und Bernsteinsäure.Optionally, the active ingredient compositions of the invention may contain 1 to 5 wt .-% buffer based on the total amount of the formulation prepared for pH regulation, wherein the amount and type of buffer used depends on the chemical properties of the active ingredient or the active ingredients. Examples of buffers are alkali salts of weak inorganic or organic acids such. For example, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.
Je nach Art des enthaltenen Wirkstoffs bzw. Effektstoffs können die erfindungsgemäßen Wirkstoff- bzw. Effektstoffzusammensetzungen in an sich vergleichbare Weise konventionelle Formulierungen des jeweiligen Wirk- bzw. Effektstoffs eingesetzt wer- den. Beispielsweise können Wirkstoffzusammensetzungen, die wenigstens einen in- sektiziden, akarziden oder nematiziden Wirkstoff enthalten, zur Bekämpfung von schädlichen Insekten, Acariden, oder Nematoden eingesetzt werden. Wenn die erfindungsgemäßen Wirkstoffzusammensetzungen wenigstens einen fungiziden Wirkstoff enthalten, können sie zur Bekämpfung von Schadpilzen eingesetzt werden. Wenn die erfindungsgemäßen Wirkstoffzusammensetzungen einen herbiziden Wirkstoff enthalten, können sie zur Bekämpfung von Ungräsern und dergleichen eingesetzt werden.Depending on the nature of the active substance or effect substance contained, the active substance or effect substance compositions according to the invention can be used in a manner comparable to conventional formulations of the particular active substance or effect substance. For example, active ingredient compositions containing at least one insecticidal, acaricidal or nematicidal active ingredient can be used to control harmful insects, acarids, or nematodes. If the active ingredient compositions according to the invention contain at least one fungicidal active ingredient, they can be used to combat harmful fungi. When the active compound compositions according to the invention contain a herbicidal active ingredient, they can be used for combating grass weeds and the like.
Je nach Art des Wirkstoffs werden die erfindungsgemäßen Zusammensetzungen insbesondere zum Schutz von Pflanzen vor einem Befall mit Schadorganismen wie Insek- ten, Acarina, Nematoden, oder zum Schutz vor einem Befall mit pflanzenpathogenen Pilzen und dergleichen, oder bei der Saatgutbehandlung oder im Materialschutz eingesetzt, beispielsweise zum Schutz von Lignocellulosematerialien wie Holz, vor einem Befall mit Schadinsekten, wie holzzerstörende Käfer, Termiten, Ameisen und dergleichen, oder vor einem Befall mit holzverfärbenden oder holzzerstörenden Pilzen.Depending on the nature of the active ingredient, the compositions according to the invention are used in particular for protecting plants against attack by harmful organisms such as insects, acarina, nematodes or for protection against infestation with phytopathogenic fungi and the like, or in seed treatment or in material protection, for example for the protection of lignocellulosic materials such as wood, against infestation with noxious insects, such as wood-destroying beetles, termites, ants and the like, or against infestation with wood-discoloring or wood-destroying fungi.
Selbstverständlich können die erfindungsgemäßen Zusammensetzungen auch in der Kosmetik oder in der Medizin oder in technischen Anwendungen eingesetzt werden.Of course, the compositions according to the invention can also be used in cosmetics or in medicine or in technical applications.
Die Erfindung soll nun anhand der folgenden Beispiele näher erläutert werden. I. Herstellung der amphiphilen Polymerzusammensetzung:The invention will now be explained in more detail with reference to the following examples. I. Preparation of the amphiphilic polymer composition:
1.1 Herstellungsbeispiel 1 : 1444 g Tetrahydrofuran wurden unter Rückfluss erhitzt. Innerhalb von 2 Stunden, gab man gleichzeitig Zulauf 1a, bestehend aus 2109 g Methylmethacrylat und 703 g Styrol, sowie Zulauf 1 b, bestehend aus 1444 g Tetrahydrofuran (THF), 18,6 g Azobisisobutyronit. il (AIBN) und 58,4 g Mercaptoethanol, zu und hielt die Mischung 24 h unter Rückfluss. Dann gab man 430 g eines handelsüblichen Biu- rets des Hexamethylendiisocyanat (NCO-Gehalt von 22 %, Viskosität bei 23 °C von 4,0 Pa.s) und 0,1 g Dibutylzinndilaurat zu und rührte die Reaktionsmischung unter Beibehaltung der Temperatur so lange, bis der NCO-Gehalt der Mischung auf 1 ,02 % gefallen ist. Anschließend gab man zu der Mischung 3000 g eines Methyl-terminierten Polyethylenoxids (zahlenmittleres Molekulargewicht 2000 Dalton, KOH-Zahl 33 mg/g Festsubstanz) und rührte die Reaktionsmischung unter Beibehaltung der Temperatur so lange, bis der NCO-Gehalt 0 % betrug. Dann gab man innerhalb von 30 min 14,7 kg Wasser zu und destillierte Tetrahydrofuran unter vermindertem Druck ab. Auf diese Weise erhielt man eine 30 gew.- %ige wässrige Dispersion der amphiphilen Polymerzusammensetzung mit einer mittleren Teilchengröße von 50 nm (bestimmt durch dynamische Lichtstreuung).1.1 Production Example 1: 1444 g of tetrahydrofuran were heated under reflux. Within 2 hours, were simultaneously feed 1a, consisting of 2109 g of methyl methacrylate and 703 g of styrene, and feed 1 b, consisting of 1444 g of tetrahydrofuran (THF), 18.6 g of azobisisobutyronite. il (AIBN) and 58.4 g of mercaptoethanol, and kept the mixture under reflux for 24 h. Then, 430 g of a commercially available biuret of hexamethylene diisocyanate (NCO content of 22%, viscosity at 23 ° C. of 4.0 Pa.s) and 0.1 g of dibutyltin dilaurate were added, and the reaction mixture was stirred while maintaining the temperature until the NCO content of the mixture has fallen to 1, 02%. Then, 3000 g of a methyl-terminated polyethylene oxide (number-average molecular weight 2000 daltons, KOH number 33 mg / g solid substance) was added to the mixture and the reaction mixture was stirred while maintaining the temperature until the NCO content became 0%. 14.7 kg of water were then added over 30 minutes, and tetrahydrofuran was distilled off under reduced pressure. In this way, a 30% by weight aqueous dispersion of the amphiphilic polymer composition having an average particle size of 50 nm (determined by dynamic light scattering) was obtained.
1.2 Herstellungsbeispiel 2:1.2 Production Example 2:
1444 g THF wurden unter Rückfluss erhitzt. Innerhalb von 2 Stunden, gab man gleichzeitig Zulauf 1 a, bestehend aus 2109 g Methylmethacrylat und 703 g Styrol, sowie Zulauf 1b, bestehend aus 1444 g Tetrahydrofuran, 18,6 AIBN und 58,4 g Mercaptoethanol, zu und hielt die Mischung 24 h unter Rückfluss. Dann gab man 167 g Isophorondiisocyanat und 0,7 g Dibutylzinndilaurat zu und rührte die Reaktionsmischung unter Beibehaltung der Temperatur so lange, bis der NCO-Gehalt auf 0,53 % gefallen ist. Anschließend gab man zu der Mischung 1500 g eines Methyl-terminierten Polyethylenoxids (zahlenmittleres Molekulargewicht 2000 Dalton, KOH-Zahl 33 mg/g Festsubstanz) und rührte die Reaktionsmischung unter Beibehaltung der Temperatur so lange, bis der NCO-Gehalt 0 % betrug. Dann gab man innerhalb von 30 min 10,6 kg Wasser zu und destil- lierte Tetrahydrofuran unter vermindertem Druck ab. Auf diese Weise erhielt man eine 30 gew.-%ige wässrige Dispersion der amphiphilen Polymerzusammensetzung mit einer mittleren Teilchengröße von 52 nm (bestimmt durch dynamische Lichtstreuung).1444 g of THF were heated to reflux. Within 2 hours, were simultaneously feed 1 a, consisting of 2109 g of methyl methacrylate and 703 g of styrene, and feed 1b, consisting of 1444 g of tetrahydrofuran, 18.6 AIBN and 58.4 g of mercaptoethanol, and kept the mixture for 24 h under reflux. Then 167 g of isophorone diisocyanate and 0.7 g of dibutyltin dilaurate were added and the reaction mixture was stirred while maintaining the temperature until the NCO content had fallen to 0.53%. Then, 1500 g of a methyl-terminated polyethylene oxide (number-average molecular weight 2000 daltons, KOH number 33 mg / g solid substance) was added to the mixture, and the reaction mixture was stirred while maintaining the temperature until the NCO content became 0%. 10.6 kg of water were then added over 30 minutes, and distilled tetrahydrofuran under reduced pressure. In this way, a 30% by weight aqueous dispersion of the amphiphilic polymer composition having an average particle size of 52 nm (determined by dynamic light scattering) was obtained.
I.3 Herstellungsbeispiel 3: 1444 g THF wurden unter Rückfluss erhitzt. Innerhalb von 2 Stunden, gab man gleichzeitig Zulauf 1a, bestehend aus 2109 g Methylmethacrylat und 703 g Styrol, sowie Zulauf 1b, bestehend aus 1444 g Tetrahydrofuran, 18,6 AIBN und 5 58,4 g Mercaptoethanol, zu und hielt die Mischung 24 h unter Rückfluss. Dann gab man 430 g eines handelsüblichen Biurets des Hexamethylendiisocyanat (NCO-Gehalt von 22 %, Viskosität bei 23 °C von 4,0 Pa.s), 3000 g eines Methyl- terminierten Polyethylenoxids (zahlenmittleres Molekulargewicht 2000 Dalton, KOH-Zahl 33 mg/g Festsubstanz) und 0,87 g Dibutylzinndilaurat zu und rührte o die Reaktionsmischung unter Beibehaltung der Temperatur so lange, bis der NCO-Gehalt 0 % betrug. Dann gab man innerhalb von 30 min 14,7 kg Wasser zu und destillierte Tetrahydrofuran unter vermindertem Druck ab. Auf diese Weise erhielt man eine 30 gew.-%ige wässrige Dispersion der amphiphilen Polymerzusammensetzung mit einer mittleren Teilchengröße von 52 nm (bestimmt durch5 dynamische Lichtstreuung).I.3 Production Example 3 1444 g of THF were heated to reflux. Within 2 hours, were simultaneously feed 1a, consisting of 2109 g of methyl methacrylate and 703 g of styrene, and feed 1b, consisting of 1444 g of tetrahydrofuran, 18.6 AIBN and 5 58.4 g mercaptoethanol, and kept the mixture for 24 h under reflux. Then 430 g of a commercial biuret of hexamethylene diisocyanate (NCO content of 22%, viscosity at 23 ° C of 4.0 Pa.s), 3000 g of a methyl-terminated polyethylene oxide (number average molecular weight 2000 daltons, KOH number 33 mg / g solid substance) and 0.87 g of dibutyltin dilaurate, and the reaction mixture was stirred while maintaining the temperature until the NCO content was 0%. 14.7 kg of water were then added over 30 minutes, and tetrahydrofuran was distilled off under reduced pressure. In this way, a 30% by weight aqueous dispersion of the amphiphilic polymer composition having an average particle size of 52 nm (determined by 5 dynamic light scattering) was obtained.
I.4 Herstellungsbeispiel 4:I.4 Production Example 4
430 g des in Herstellungsbeispiel 1 eingesetzten handelsüblichen Biurets des0 Hexamethylendiisocyanats, 3000 g eines methylterminierten Polyethylenoxids (OH-Zahl 33 mg KOH/g Festsubstanz) und 117 mg Dibutylzinndilaurat wurden in 3430 g Tetrahydrofuran gelöst. Die Lösung wurde solange bei Rückflusstemperatur gerührt, bis der NCO-Gehalt 0,46 % betrug. 5 1444 g THF wurden unter Rückfluss erhitzt. Innerhalb von 2 Stunden gab man gleichzeitig Zulauf 1a, bestehend aus 2109 g Methylmethacrylat und 703 g Styrol, sowie Zulauf 1 b, bestehend aus 1444 g Tetrahydrofuran, 18,6 g AIBN und 58,4 g Mercaptoethanol, zu und hielt die Mischung 24 h unter Rückfluss. Dann gab man das zwischenzeitlich hergestellte Umsetzungsprodukt aus Biuret des Hexamethy-0 lendiisocyanats mit einem methylterminierten Polyethylenoxids hinzu und rührte die Reaktionsmischung unter Beibehaltung der Temperatur so lange, bis der NCO-Gehalt 0 % betrug. Dann gab man innerhalb von 30 min. 14,7 kg Wasser zu und destillierte Tetrahydrofuran im Vakuum ab. Auf diese Weise erhielt man eine 30 %ige wässrige Dispersion der amphiphilen Polymerzusammensetzung (Teil-5 chengröße 129 nm, gemessen mit dynamischer Lichtstreuung).430 g of the commercially available biuret des0 hexamethylene diisocyanate used in Preparation Example 1, 3000 g of a methyl-terminated polyethylene oxide (OH number 33 mg KOH / g solid) and 117 mg of dibutyltin dilaurate were dissolved in 3430 g of tetrahydrofuran. The solution was stirred at reflux temperature until the NCO content was 0.46%. 5,144 g of THF were heated to reflux. In the course of 2 hours, feed 1a, consisting of 2109 g of methyl methacrylate and 703 g of styrene, and feed 1b, consisting of 1444 g of tetrahydrofuran, 18.6 g of AIBN and 58.4 g of mercaptoethanol, were added simultaneously and the mixture was kept for 24 h under reflux. Then added to the meantime prepared reaction product of biuret of Hexamethy-0 lendiisocyanats with a methyl-terminated polyethylene oxide and stirred the reaction mixture while maintaining the temperature until the NCO content was 0%. Then you gave within 30 min. 14.7 kg of water and distilled tetrahydrofuran in vacuo. In this way, a 30% aqueous dispersion of the amphiphilic polymer composition (particle size 129 nm, measured with dynamic light scattering) was obtained.
II. Herstellung erfindungsgemäßer wässriger WirkstoffzubereitungenII. Preparation of aqueous active compound preparations according to the invention
11.1 Analytik:0 Die hier angegebenen Viskositäten wurden in einem Rotationsviskosimeter nach DIN 53019-2 bestimmt.11.1 Analytics: 0 The viscosities stated here were determined in a rotational viscometer according to DIN 53019-2.
Die Bestimmung der mittleren Teilchendurchmesser erfolgte nach der Methode der statischen Lichtstreuung an einer verdünnten Probe der wässrigen Wirkstoffformulierung bei 20 °C.The average particle diameter was determined by the method of static light scattering on a diluted sample of the aqueous active ingredient formulation at 20 ° C.
Zur Prüfung der Lagerungsstabilität wurden die wässrigen Wirkstoffzusammensetzungen 2 Wochen bei 54 °C und 2 Wochen bei 5 °C gelagert. Außerdem wur- den die Wirkstoff Zusammensetzungen eingefroren und wieder aufgetaut. Lagerstabilität ist dann gegeben, wenn unter diesen Bedingungen weder Sedimentation noch ein Aufrahmen beobachtet wird.In order to test storage stability, the aqueous active compound compositions were stored at 54 ° C. for 2 weeks and at 5 ° C. for 2 weeks. In addition, the active ingredient compositions were frozen and thawed again. Storage stability is given when neither sedimentation nor creaming is observed under these conditions.
II.2 Allgemeine Herstellungsvorschriften:II.2 General manufacturing instructions:
1. Solubilisierungsmethode (flüssige Wirkstoffe und Wirkstoffschmelzen): 10 g Wirkstoff werden in 90 g einer wässrigen Dispersion einer amphiphilen Polymerzusammensetzung, enthaltend 30 g Polymer, bei einer Temperatur eingerührt, bei welcher der Wirkstoff als niedrigviskose Schmelze vorliegt. Je nach Viskosität von Polymerlösung und Wirkstoffschmelze erfolgt das Einrühren unter Verwendung eines Magnetrührers oder eines Ultraturrax. Die erforderliche Zeit bis zum Solubilisierungsgleichgewicht ist abhängig von der Polymerzusammensetzung und vom Wirkstoff und kann wenige Sekunden aber auch einige Stunden dauern. Das Solubilisierungsgleich- gewicht ist erreicht, wenn sich der Wirkstoff gleichmäßig in der Mischung verteilt hat und trotz weiterem Energieeintrag keine Änderung der Teilchengröße beobachtet wird.1. Solubilization method (liquid active ingredients and active ingredient melts): 10 g of active ingredient are stirred into 90 g of an aqueous dispersion of an amphiphilic polymer composition containing 30 g of polymer at a temperature at which the active ingredient is present as a low-viscosity melt. Depending on the viscosity of the polymer solution and the active ingredient melt, the stirring is carried out using a magnetic stirrer or an Ultraturrax. The time required for the solubilization equilibrium depends on the polymer composition and on the active substance and can take a few seconds but also a few hours. The solubilization equilibrium is reached when the active ingredient has distributed uniformly in the mixture and no change in particle size is observed despite further energy input.
2. Phaseninversionsmethode: 10 g des flüssigen oder festen Wirkstoffs und 30 g der amphiphilen Polymerzusammensetzung (Polymergehalt > 95 Gew.-%) werden in einem organischen Lösemittel gelöst, welches einen Siedepunkt unter 100 °C hat (z. B. Tetrahydrofuran). Dann wird unter Rühren Wasser zugegeben und anschließend wird das organische Lösemittel destillativ entfernt. Es wird soviel Wasser zugegeben, dass die resultierende wässrige Formulierung 10 gew.-%ig an Wirkstoff und 30 gew.-%ig an Polymer ist.2. Phase Inversion Method: 10 g of the liquid or solid active ingredient and 30 g of the amphiphilic polymer composition (polymer content> 95% by weight) are dissolved in an organic solvent having a boiling point below 100 ° C (eg tetrahydrofuran). Then, while stirring, water is added and then the organic solvent is removed by distillation. So much water is added that the resulting aqueous formulation is 10% by weight of active ingredient and 30% by weight of polymer.
3. Methode der festen Lösung: 0.5 g der amphiphilen Polymerzusammensetzung (Polymergehalt > 95 Gew.-%) und 0,1 g des Wirkstoffs werden in ca. 20 ml Dimethylfor- mamid gelöst. Anschließend wird das Lösemittel vollständig entfernt (z. B. am Rotationsverdampfer), so dass eine feste Lösung aus hydrophobem Wirkstoff und amphiphiler Polymerzusammensetzung zurückbleibt. Eine gepufferte wässrige Lösung (100 ml, pH 6,8) wird zugegeben und die Mi- schung 24 Stunden gerührt. Nach Filtrieren wird die Lösung mittels HPLC (UV-Detektor) analysiert und die Konzentration des Wirkstoffs bestimmt.3. Method of solid solution: 0.5 g of the amphiphilic polymer composition (polymer content> 95% by weight) and 0.1 g of the active compound are dissolved in about 20 ml of dimethylformamide. Mamid solved. Thereafter, the solvent is completely removed (eg, on a rotary evaporator) to leave a solid solution of hydrophobic drug and amphiphilic polymer composition. A buffered aqueous solution (100 ml, pH 6.8) is added and the mixture is stirred for 24 hours. After filtration, the solution is analyzed by means of HPLC (UV detector) and the concentration of the active ingredient is determined.
4. Düsenfällung: Eine 30 %ige wässrige Polymerdispersion wird mit einer 40 %igen Wirk- stoff/THF-Lösung mittels zwei Pumpen in einer Mischvorrichtung über eine Mischdüse zusammengemischt. Der Durchsatz der Polymerdispersion beträgt 12 kg/h, der Durchsatz der THF-Lösung beträgt 3 kg/h, so dass der Gesamtdurchsatz bei 15 kg/h liegt. Die Mischvorrichtung ist vergleichbar mit der in „Handbook of Industrial Crystallization" (A. S. Myerson, 1993 Butterworth-Heinemann, Seite 139, ISBN 0-7506-9155-7) beschriebene Apparatur. Man erhielt eine hellgelbe milchige Suspension mit 8 % Wirkstoff und 24 % Polymer. Anschließend wird THF und ein Teil des Wassers destillativ entfernt, so dass eine wässrige nanopartikuläre Formulierung mit 10 % Wirkstoff und 30 % Polymer entsteht.4. Nozzle Precipitation: A 30% aqueous polymer dispersion is mixed with a 40% active / THF solution via two pumps in a mixing device via a mixing nozzle. The throughput of the polymer dispersion is 12 kg / h, the throughput of the THF solution is 3 kg / h, so that the total throughput is 15 kg / h. The mixing device is comparable to the apparatus described in "Handbook of Industrial Crystallization" (AS Myerson, 1993 Butterworth-Heinemann, page 139, ISBN 0-7506-9155-7) to give a light yellow milky suspension with 8% active ingredient and 24%. Subsequently, THF and part of the water are removed by distillation to give an aqueous nanoparticulate formulation with 10% active ingredient and 30% polymer.
11.3 Formulierbeispiel 1 : Solubilisierung von Pyraclostrobin nach der Phaseninversionsmethode (allgemeine Vorschrift 2)11.3 Formulation Example 1: Solubilization of Pyraclostrobin by the Phase Inversion Method (General Procedure 2)
10 g Pyraclostrobin wurden zusammen mit 30 g amphiphiler Polymerzusammen- setzung aus Beispiel 2 in 100 g THF gelöst. Dann gab man unter Rühren Wasser zu und entfernte das THF unter vermindertem Druck. Die Menge an Wasser war so gewählt, dass die resultierende wässrige Formulierung 10 Gew.-% Wirkstoff und 30 Gew.-% der amphiphilen Polymerzusammensetzung enthielt. Die erhaltene Wirkstoffzusammensetzung war homogen, nahezu visuell transparent, mindestens mehrere Monate sedimentationsstabil und ließ sich mit Wasser (sowohl mit vollentsalztem Wasser und Wasser 10°dH) verdünnen, ohne dass eine Sedimentation oder eine Kristallisation des Wirkstoffs auftrat. Die disperse Phase (Polymer/ Wirkstoff-Partikel) hatte eine sphärische Struktur und wies einen mittleren Durchmesser, bestimmt durch Lichtstreuung, von ca. 30 nm auf.10 g of pyraclostrobin were dissolved together with 30 g of amphiphilic polymer composition from Example 2 in 100 g of THF. Water was added with stirring and the THF removed under reduced pressure. The amount of water was chosen so that the resulting aqueous formulation contained 10% by weight of active ingredient and 30% by weight of the amphiphilic polymer composition. The active ingredient composition obtained was homogeneous, almost visually transparent, stable to sedimentation for at least several months and was diluted with water (both with demineralized water and water at 10 ° dH) without any sedimentation or crystallization of the active ingredient occurring. The disperse phase (polymer / drug particle) had a spherical structure and had an average diameter, determined by light scattering, of about 30 nm.
11.4 Formulierungsbeispiel 2: Solubilisierung von Pyraclostrobin nach der Solubilisie- rungsmethode (allgemeine Vorschrift 1 ) Pyraclostrobin ist bei 70 °C eine gut fließende Schmelze (Viskosität 2200 mPas) und wurde auch nach der allgemeinen Vorschrift 1 bei einer Temperatur von 70 °C formuliert. Die erhaltene Wirkstoffzusammensetzung war homogen, nahezu visuell transparent, mindestens mehrere Monate sedimentationsstabil und ließ sich mit Wasser (sowohl mit vollentsalztem Wasser und Wasser 10°dH) verdünnen, ohne dass eine Sedimentation oder eine Kristallisation des Wirkstoffs auftrat.11.4 Formulation Example 2: Solubilization of Pyraclostrobin by the Solubilization Method (General Procedure 1) Pyraclostrobin is at 70 ° C a good-flowing melt (viscosity 2200 mPas) and was also formulated according to general rule 1 at a temperature of 70 ° C. The active ingredient composition obtained was homogeneous, almost visually transparent, stable to sedimentation for at least several months and was diluted with water (both with demineralized water and water at 10 ° dH) without any sedimentation or crystallization of the active ingredient occurring.
Die disperse Phase (Polymer/ Wirkstoff-Partikel) hatte eine sphärische Struktur und wies einen mittleren Durchmesser, bestimmt durch Lichtstreuung, von ca. 30 nm auf.The disperse phase (polymer / drug particle) had a spherical structure and had an average diameter, determined by light scattering, of about 30 nm.
11.5 Formulierbeispiel 3: Solubilisierung von Pyraclostrobin nach der Düsenfällung (allgemeine Vorschrift 4)11.5 Formulation Example 3: Solubilization of Pyraclostrobin after Jet Precipitation (General Procedure 4)
Pyraclostrobin wurde nach der allgemeinen Vorschrift 4 formuliert. Die erhaltene Wirkstoffzusammensetzung war homogen, nahezu visuell transparent, mindestens mehrere Monate sedimentationsstabil und ließ sich mit Wasser (sowohl mit vollentsalztem Wasser und Wasser 10°dH) verdünnen, ohne dass eine Sedimentation oder eine Kristallisation des Wirkstoffs auftrat.Pyraclostrobin was formulated according to general procedure 4. The active ingredient composition obtained was homogeneous, almost visually transparent, stable to sedimentation for at least several months and was diluted with water (both with demineralized water and water at 10 ° dH) without any sedimentation or crystallization of the active ingredient occurring.
11.6 Formulierbeispiel 4: Solubilisierung von Metconazol nach der Phaseninversionsmethode (allgemeine Vorschrift 2) 10 g Metconazol, ein Feststoff mit Schmelzpunkt von 110 bis 113 °C, wurden zusammen mit 30 g amphiphiler Polymerzusammensetzung aus Beispiel 1 in 100 g THF gelöst. Dann gab man unter Rühren Wasser zu und entfernte das THF unter vermindertem Druck. Die Menge an Wasser war so gewählt, dass die resultierende wässrige Formulierung 10 Gew.-% Wirkstoff und 30 Gew.-% der amphiphi- len Polymerzusammensetzung enthielt.11.6 Formulation Example 4: Solubilization of Metconazole by the Phase Inversion Method (General Procedure 2) 10 g of metconazole, a solid having a melting point of 110 to 113 ° C., were dissolved in 100 g of THF together with 30 g of the amphiphilic polymer composition from Example 1. Water was added with stirring and the THF removed under reduced pressure. The amount of water was chosen so that the resulting aqueous formulation contained 10% by weight of active ingredient and 30% by weight of the amphiphilic polymer composition.
Die erhaltene Wirkstoffzusammensetzung war homogen, nahezu visuell transparent, mindestens mehrere Monate sedimentationsstabil und ließ sich mit Wasser (sowohl mit vollentsalztem Wasser und Wasser 10°dH) verdünnen, ohne dass eine Sedimentation oder eine Kristallisation des Wirkstoffs auftrat. Die disperse Phase (Polymer/Wirkstoff-Partikel) hatte eine sphärische Struktur und wies einen mittleren Durchmesser, bestimmt durch Lichtstreuung, von ca. 30 nm auf.The active ingredient composition obtained was homogeneous, almost visually transparent, stable to sedimentation for at least several months and was diluted with water (both with demineralized water and water at 10 ° dH) without any sedimentation or crystallization of the active ingredient occurring. The disperse phase (polymer / drug particle) had a spherical structure and had an average diameter, determined by light scattering, of about 30 nm.
In analoger Weise können auch die anderen in Tabelle 1 angegebenen Wirkstof- fe formuliert werden. Tabelle 1In an analogous manner, the other active ingredients specified in Table 1 can also be formulated. Table 1
Figure imgf000048_0001
.7 Formulierbeispiel 5: Solubilisierung von Vitamin A - Acetat nach der Phaseninversionsmethode (allgemeine Vorschrift 2)
Figure imgf000048_0001
.7 Formulation Example 5: Solubilization of Vitamin A - Acetate by the Phase Inversion Method (General Procedure 2)
10 g Vitamin A - Acetat wurden zusammen mit 30 g amphiphiler Polymerzusammensetzung aus Beispiel 1 in 100 g THF gelöst. Dann gab man unter Rühren Wasser zu und entfernte das THF unter vermindertem Druck. Die Menge an Wasser war so gewählt, dass die resultierende wässrige Formulierung 10 Gew.- % Wirkstoff und 30 Gew.-% der amphiphilen Polymerzusammensetzung enthielt.10 g of vitamin A acetate were dissolved together with 30 g of amphiphilic polymer composition from Example 1 in 100 g of THF. Water was added with stirring and the THF removed under reduced pressure. The amount of water was chosen so that the resulting aqueous formulation contained 10% by weight of active ingredient and 30% by weight of the amphiphilic polymer composition.
Die erhaltene Wirkstoffzusammensetzung war homogen, nahezu visuell transparent, mindestens mehrere Monate sedimentationsstabil und ließ sich mit Wasser (sowohl mit vollentsalztem Wasser und Wasser 10°dH) verdünnen, ohne dass eine Sedimentation oder eine Kristallisation des Wirkstoffs auftrat.The active ingredient composition obtained was homogeneous, almost visually transparent, stable to sedimentation for at least several months and was diluted with water (both with demineralized water and water at 10 ° dH) without any sedimentation or crystallization of the active ingredient occurring.
Anwendungstechnische PrüfungApplication testing
III.1 Überprüfung der fungiziden WirksamkeitIII.1 Verification of fungicidal activity
Die wässrige Wirkstoffzusammensetzung aus Formulierungsbeispiel 1 wurde mit zwei kommerziellen Formulierungen des gleichen Wirkstoffs Pyraclostrobin bezüglich ihrer Aktivität gegen Phytophthora infestans an Tomaten im Gewächshaus gemäß folgender Vorschrift verglichen (Präventivtest, protektive Wirksamkeit):The aqueous active substance composition from Formulation Example 1 was compared with two commercial formulations of the same active ingredient pyraclostrobin with regard to their activity against Phytophthora infestans on tomatoes in the greenhouse according to the following procedure (preventive test, protective activity):
Die Wirkstoffformulierungen wurden mit Leitungswasser auf die gewünschte Wirkstoffkonzentrationen (zwischen 4 und 250 ppm) verdünnt. Die Applikation auf Tomatenpflanzen erfolgte in einer Spritzkabine mit 25 ml Volumen, welches einer praxisüblichen Wassermenge von ca. 500 l/ha entspricht. Der Standardpilz (Phytophthora infestans) wurde 7 Tage nach Behandlung inokuliert. Die Versuchspflanzen wurden im Gewächshaus bei 18 bis 20 °C und 90 % relativer Luftfeuchte aufgestellt. Die Bonitur erfolgte 5 Tage nach Inokulation durch Bestimmung des prozentualen Befalls der Blätter.The drug formulations were diluted with tap water to the desired drug concentrations (between 4 and 250 ppm). The application on tomato plants was carried out in a spray booth with 25 ml volume, which corresponds to a practical amount of water of about 500 l / ha. The standard mushroom (Phytophthora infestans) was inoculated 7 days after treatment. The test plants were placed in the greenhouse at 18 to 20 ° C and 90% relative humidity. The assessment was made 5 days after inoculation by determining the percentage of attack of the leaves.
Die Ergebnisse der biologischen Prüfung sind in Tabelle 2 zusammengefasst. Die Ergebnisse zeigen, dass der in den Polymerpartikeln stabilisierte Wirkstoff eine fungizide Aktivität auf dem Niveau kommerzieller Produkte aufweist.The results of the biological test are summarized in Table 2. The results show that the drug stabilized in the polymer particles has a fungicidal activity at the level of commercial products.
Tabelle 2: Phytophthora infestans - Befall [%] an Tomaten nach fünf Tagen als Funktion des WirkstoffgehaltsTable 2: Phytophthora infestans - infection [%] of tomatoes after five days as a function of the active substance content
Figure imgf000049_0001
Figure imgf000049_0001
1 ) EC-Formulierung: 23,5 Gew.-% Pyraclostrobin, 4,7 Gew.-% anionisches Netzmittel und 4,7 Gew.-% nichtionisches Netzmittel in 67,1 Gew.-% eines aromatischen Lösungsmittels 1) EC formulation: 23.5 wt% pyraclostrobin, 4.7 wt% anionic surfactant and 4.7 wt% nonionic surfactant in 67.1 wt% of an aromatic solvent

Claims

Patentansprüche: claims:
1. Amphiphile Polymerzusammensetzung, erhältlich durch Umsetzung von a) wenigstens einem hydrophoben Polymer P1 , das gegenüber Isocyanatgruppen reaktive funktionelle Gruppen RP1 trägt und das aus ethyleniseh ungesättigten Monomeren M1 aufgebaut ist, umfassend: a1 ) wenigstens 10 Gew.-%, bezogen auf die Gesamtmenge der Monome- re M1 , Monomere M1 a der allgemeinen Formel IAn amphiphilic polymer composition obtainable by reacting a) at least one hydrophobic polymer P1 which carries isocyanate-reactive functional groups R P1 and which is made up of ethylenically unsaturated monomers M1, comprising: a1) at least 10% by weight, based on the Total amount of monomers M1, monomers M1 a of the general formula I
Figure imgf000050_0001
worin X für Sauerstoff oder eine Gruppe N-R4 steht; R1 C Cιo-Alkyl, C5-C10-Cycloalkyl, Phenyl oder Phenyl-Cι-C4-alkyl steht; R2 Wasserstoff oder Cι-C4-Alkyl bedeutet; R3 Wasserstoff oder d-C4-Alkyl bedeutet; und R4 Wasserstoff oder Cι-C4-Alkyl bedeutet; a2) bis zu 90 Gew.-%, bezogen auf die Gesamtmenge der Monomere M1 , neutrale, monoethylenisch ungesättigte Monomere M1b, deren Wasserlöslichkeit bei 25°C weniger als 50 g/l beträgt und die von den Monomeren M1 a verschieden sind; und a3) bis zu 30 Gew.-%, bezogen auf die Gesamtmenge der Monomere M1 , ethyleniseh ungesättigte Monomeren M1c, die von den Monomeren M1 a und M1 b verschieden sind, b) wenigstens einem hydrophilen Polymer P2, das gegenüber Isocyanatgruppen reaktive funktionelle Gruppen RP2 trägt, c) mit wenigstens einer Isocyanatgruppen enthaltenden Verbindung V, die bezüglich der Isocyanatgruppen eine Funktionalität von wenigstens 1 ,5 auf- weist.
Figure imgf000050_0001
wherein X is oxygen or a group NR 4 ; R 1 C is Cιo-alkyl, C 5 -C 10 -cycloalkyl, phenyl or phenyl-C 4 -C 4 -alkyl; R 2 is hydrogen or C 1 -C 4 -alkyl; R 3 is hydrogen or C 1 -C 4 alkyl; and R 4 is hydrogen or C 1 -C 4 -alkyl; a2) up to 90% by weight, based on the total amount of monomers M1, of neutral, monoethylenically unsaturated monomers M1b whose solubility in water at 25 ° C. is less than 50 g / l and which are different from the monomers M1a; and a3) up to 30% by weight, based on the total amount of the monomers M1, of ethylenically unsaturated monomers M1c which are different from the monomers M1a and M1b, b) at least one hydrophilic polymer P2, the isocyanate-reactive functional groups R P2 bears, c) with at least one isocyanate group-containing compound V which has a functionality of at least 1.5 with respect to the isocyanate groups.
2. Polymerzusammensetzung nach Anspruch 1 , worin das hydrophobe Polymer bezüglich der funktionellen Gruppen RP1 eine Funktionalität F1 im Bereich von 0,5 bis 1 ,5 besitzt.The polymer composition of claim 1, wherein the hydrophobic polymer has a functionality F1 in the range of 0.5 to 1.5 with respect to the functional groups R P1 .
3. Polymerzusammensetzung nach einem der vorhergehenden Ansprüche, worin das hydrophobe Polymer P1 ein zahlenmittleres Molekulargewicht im Bereich von 500 bis 20000 Dalton aufweist.A polymer composition according to any one of the preceding claims, wherein the hydrophobic polymer P1 has a number average molecular weight in the range of 500 to 20,000 daltons.
4. Polymerzusammensetzung nach einem der vorhergehenden Ansprüche, worin das hydrophile Polymer keine ionischen Gruppen aufweist.A polymer composition according to any one of the preceding claims, wherein the hydrophilic polymer has no ionic groups.
5. Polymerzusammensetzung nach Anspruch 4, worin das hydrophile Polymer P2 ein aliphatischer Polyether ist, der zu wenigstens 70 Gew.-% aus Ethylenoxid- Gruppen aufgebaut ist.5. The polymer composition of claim 4, wherein the hydrophilic polymer P2 is an aliphatic polyether composed of at least 70% by weight of ethylene oxide groups.
6. Polymerzusammensetzung nach einem der vorhergehenden Ansprüche, worin das hydrophile Polymer P2 bezüglich der funktionellen Gruppen RP eine Funktionalität F2 im Bereich von 0,5 bis 3,0 besitzt.A polymer composition according to any preceding claim, wherein the hydrophilic polymer P2 has a functionality F2 in the range of 0.5 to 3.0 with respect to the functional groups R P.
7. Polymerzusammensetzung nach einem der vorhergehenden Ansprüche, worin das hydrophile Polymer P2 ein zahlenmittleres Molekulargewicht im Bereich von 500 bis 20000 Dalton aufweist.A polymer composition according to any one of the preceding claims, wherein the hydrophilic polymer P2 has a number average molecular weight in the range of 500 to 20,000 daltons.
8. Polymerzusammensetzung nach einem der vorhergehenden Ansprüche, worin man das hydrophobe Polymer P1 und das hydrophile Polymer P2 in einem Gewichtsverhältnis P1 :P2 im Bereich von 1 :10 bis 10:1 einsetzt.8. A polymer composition according to any one of the preceding claims, wherein the hydrophobic polymer P1 and the hydrophilic polymer P2 are used in a weight ratio P1: P2 in the range of 1:10 to 10: 1.
9. Verfahren zur Herstellung einer amphiphilen Polymerzusammensetzung nach einem der vorhergehenden Ansprüche, umfassend die Umsetzung i) wenigstens eines hydrophoben Polymers P1 , das aus ethyleniseh ungesättigten Monomeren M1 aufgebaut ist und das gegenüber Isocyanatgruppen reaktive funktionelle Gruppen RP1 trägt, und ii) wenigstens eines hydrophilen Polymers P2, das gegenüber Isocyanatgruppen reaktive funktionelle Gruppen trägt RP2, mit iii) wenigstens einer Isocyanatgruppen enthaltenden Verbindung V, die bezüglich der Isocyanatgruppen eine Funktionalität von wenigstens 1 ,5 aufweist. A process for the preparation of an amphiphilic polymer composition according to any one of the preceding claims which comprises reacting i) at least one hydrophobic polymer P1 made up of ethylenically unsaturated monomers M1 carrying isocyanate reactive functional groups R P1 and ii) at least one hydrophilic polymer Polymer P2, the isocyanate-reactive functional groups carries R P2 , with iii) at least one isocyanate group-containing compound V, which has a functionality of at least 1, 5 with respect to the isocyanate groups.
10. Verfahren nach Anspruch 9, worin man das Polymer P1 und das Polymer P2 nacheinander mit der Verbindung V umsetzt.10. The method according to claim 9, wherein the polymer P1 and the polymer P2 are reacted successively with the compound V.
11. Verfahren nach Anspruch 9, worin man das Polymer P1 und das Polymer P2 in einem Schritt mit der Verbindung V umsetzt.A process according to claim 9, wherein the polymer P1 and the polymer P2 are reacted in one step with the compound V.
12. Verwendung einer amphiphilen Polymerzusammensetzung nach einem der Ansprüche 1 bis 8 zur Stabilisierung von Wirkstoffen und/oder Effektstoffen, die in Wasser bei 25 °C/1013 mbar eine Löslichkeit unterhalb 10 g/l aufweisen, in ei- nem wässrigen Medium.12. Use of an amphiphilic polymer composition according to any one of claims 1 to 8 for the stabilization of active ingredients and / or effect substances which have a solubility in water at 25 ° C / 1013 mbar below 10 g / l, in an aqueous medium.
13. Verwendung einer amphiphilen Polymerzusammensetzung nach einem der Ansprüche 1 bis 8 zur Herstellung von Formulierungen von Wirkstoffen und/oder Effektstoffen, die in Wasser bei 25 °C/1013 mbar eine Löslichkeit unterhalb 10 g/l aufweisen.13. Use of an amphiphilic polymer composition according to any one of claims 1 to 8 for the preparation of formulations of active ingredients and / or effect substances which have a solubility in water at 25 ° C / 1013 mbar below 10 g / l.
14. Verwendung einer amphiphilen Polymerzusammensetzung nach einem der Ansprüche 1 bis 8 zur Herstellung wässriger Formulierungen von Wirkstoffen und Effektstoffen, die in Wasser bei 25 °C/1013 mbar eine Löslichkeit unterhalb 10 g/l aufweisen.14. Use of an amphiphilic polymer composition according to any one of claims 1 to 8 for the preparation of aqueous formulations of active ingredients and effect substances which have a solubility in water at 25 ° C / 1013 mbar below 10 g / l.
15. Wirkstoffzusammensetzung, umfassend wenigstens einen Wirkstoff und/oder Effektstoff, der in Wasser bei 25 °C/1013 mbar eine Löslichkeit unterhalb 10 g/l aufweist, und wenigstens eine amphiphile Polymerzusammensetzung nach ei- nem der Ansprüche 1 bis 8.15. Active substance composition comprising at least one active ingredient and / or effect substance which has a solubility below 10 g / l in water at 25 ° C./1013 mbar, and at least one amphiphilic polymer composition according to one of claims 1 to 8.
16. Wässrige Wirkstoffzusammensetzung, umfassend ein wässriges Medium als kontinuierliche Phase und wenigstens eine disperse Phase, enthaltend wenigstens einen Wirkstoff und/oder Effektstoff, der in Wasser bei 25 °C/1013 mbar ei- ne Löslichkeit unterhalb 10 g/l aufweist, und wenigstens eine amphiphile Polymerzusammensetzung nach einem der Ansprüche 1 bis 8.16. Aqueous active substance composition comprising an aqueous medium as the continuous phase and at least one disperse phase containing at least one active ingredient and / or effect substance which has a solubility below 10 g / l in water at 25 ° C./1013 mbar, and at least An amphiphilic polymer composition according to any one of claims 1 to 8.
17. Wirkstoffzusammensetzung nach Anspruch 16, wobei die Partikel der dispersen Phase eine mittlere Teilchengröße, bestimmt mittels dynamischer Lichtstreuung, von nicht mehr als 300 nm aufweisen.17. Active ingredient composition according to claim 16, wherein the particles of the disperse phase have an average particle size, determined by means of dynamic light scattering, of not more than 300 nm.
18. Wirkstoffzusammensetzung nach Anspruch 15, 16 oder 17, enthaltend den Wirkstoff und/oder Effektstoff und die amphiphile Polymerzusammensetzung in einem Gewichtsverhältnis von 1 :10 bis 3:1. 18. Active ingredient composition according to claim 15, 16 or 17, comprising the active ingredient and / or effect substance and the amphiphilic polymer composition in a weight ratio of 1:10 to 3: 1.
19. Wirkstoffzusammensetzung nach einem der Ansprüche 15 bis 18, mit einem Gehalt an flüchtigen organischen Verbindungen von weniger als 10 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung.19. Active ingredient composition according to any one of claims 15 to 18, having a content of volatile organic compounds of less than 10 wt .-%, based on the total weight of the composition.
20. Verfahren zur Herstellung einer Wirkstoffzusammensetzung nach einem der Ansprüche 15 bis 19, umfassend die Herstellung einer homogenen, nichtwässrigen Mischung, umfassend die amphiphile Polymerzusammensetzung und wenigstens einen Wirkstoff und/oder Effektstoff.20. A process for preparing a drug composition according to any one of claims 15 to 19, comprising preparing a homogeneous, non-aqueous mixture comprising the amphiphilic polymer composition and at least one active ingredient and / or effect substance.
21. Verfahren zur Herstellung einer wässrigen Wirkstoffzusammensetzung nach einem der Ansprüche 16 bis 19, umfassend: a) Herstellung einer homogenen, nichtwässrigen Mischung, bestehend aus amphiphiler Polymerzusammensetzung und Wirkstoff und/oder Effektstoff, und b) Dispergieren der so erhaltenen Mischung mit Wasser.21. A process for preparing an aqueous active substance composition according to any one of claims 16 to 19, comprising: a) preparing a homogeneous, non-aqueous mixture consisting of amphiphilic polymer composition and active ingredient and / or effect substance, and b) dispersing the mixture thus obtained with water.
22. Verfahren zur Herstellung einer wässrigen Wirkstoffzusammensetzung nach ei- nem der Ansprüche 16 bis 19, umfassend: a) Herstellung einer Lösung von Wirkstoff und/oder Effektstoff und gegebenenfalls amphiphiler Polymerzusammensetzung in einem organischen Lösungsmittel, das einen Siedepunkt unter dem von Wasser aufweist und b) Vermischen der Lösung des Wirkstoffs und/oder Effektstoffs mit Wasser oder einer wässrigen Lösung des amphiphilen Copolymeren und c) Entfernen des organischen Lösungsmittels.22. A process for the preparation of an aqueous active substance composition according to one of claims 16 to 19, comprising: a) preparing a solution of active ingredient and / or effect substance and optionally amphiphilic polymer composition in an organic solvent which has a boiling point below that of water and b ) Mixing the solution of the active ingredient and / or effect substance with water or an aqueous solution of the amphiphilic copolymer and c) removing the organic solvent.
23. Verfahren zur Herstellung einer wässrigen Wirkstoffzusammensetzung nach einem der Ansprüche 16 bis 19, umfassend das Einarbeiten des Wirkstoffs und/oder des Effektstoffs in eine wässrige Lösung der amphiphilen Polymerzusammensetzung bei einer Temperatur oberhalb der Schmelztemperatur des Wirkstoffs. 23. A process for the preparation of an aqueous active ingredient composition according to any one of claims 16 to 19, comprising incorporating the active ingredient and / or the effect substance in an aqueous solution of the amphiphilic polymer composition at a temperature above the melting temperature of the active ingredient.
PCT/EP2005/006106 2004-06-08 2005-06-07 Amphiphilic polymer compositions and their use WO2005121201A1 (en)

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